Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same

ABSTRACT

The present invention provides poly(ureaurethane)s including a reaction product of components comprising: (a) at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; (b) about 0.1 to about 0.9 equivalents of at least one polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups; and (c) at least one amine curing agent, wherein the reaction product components are essentially free of polyester polyol and polyether polyol; compositions, coatings and articles made therefrom and methods of making the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 10/932,641, filed on Sep. 1, 2004, and Ser. Nos.11/303,670, 11/303,422, 11/303,892, 11/303,671 and 11/303,832, each ofwhich was filed on Dec. 16, 2005. Each of the above applications isincorporated by reference herein.

BACKGROUND OF THE INVENTION

I. Field of the Invention

The present invention relates to polyurethanes and poly(ureaurethanes)prepared from branched polyols, branched polyisocyanates and/orpolyisocyanate trimers, articles and coatings prepared therefrom, andmethods of making the same.

II. Technical Considertions

A number of organic polymeric materials, for example plastics such aspolycarbonates and acrylics, have been developed as alternatives andreplacements for glass in applications such as optical lenses, fiberoptics, windows and automotive, nautical and aviation transparencies.For example, in aircraft glazings both polycarbonates, such as LEXAN®,and acrylics have enjoyed widespread acceptance. These polymericmaterials can provide advantages relative to glass, including shatter orpenetration resistance, lighter weight for a given application,flexibility, ease of molding and dyeability. Unfortunately, there aresome serious disadvantages associated with both polycarbonates andacrylics. Polycarbonates scratch easily, and if directly exposed tosunlight and harsh environments soon become difficult to view through.Acrylics, although not as scratchable as polycarbonates, do not have thephysical properties of the polycarbonates such as heat distortiontemperature and impact resistance. Some “high impact” strengthpolycarbonates can have inconsistent impact strength that can degradeover time, poor crack propagation resistance (K-factor), poor opticalquality, poor solvent resistance and poor weatherability. Even thoughpolycarbonates can exhibit good impact strength when impacted at lowspeeds, at high impact speeds of greater than about 1100 ft/sec (335.3m/sec), such as those exhibited in ballistics applications, a 9 mmbullet (125 grain) fired from about 20 feet (6.1 m) at a speed of about1350 ft/sec (411 m/sec) can pass easily through a 1 inch (2.5 cm) thickpolycarbonate plastic.

Also, polycarbonates are typically extruded, which can produce opticaldistortions in the extrudate in the direction of extrusion. For opticalapplications such as fighter plane canopies, polycarbonates typicallymust undergo an additional processing step to remove the distortions,which can increase cost. Also, some polycarbonates are birefringentwhich can also cause optical distortions. For example, the Abbe numberof LEXAN is 34. Higher Abbe values indicate better visual acuity andless chromatic aberrations.

Thus, there is a need in the art to develop polymers useful forproducing articles having good optical quality, high impact resistance,high impact strength, high K factor, good ballistics resistance, goodsolvent resistance and good weatherability. The ability to fabricatearticles by casting or reaction injection molding rather than extrusionalso is desirable.

SUMMARY OF THE INVENTION

Discussion of the various aspects and embodiments of polyurethanes andpoly(ureaurethanes) of the present invention have been grouped below.While the various aspects of the invention have been grouped fordiscussion purposes, the groupings are not intended to limit the scopeof the invention and aspects of one grouping may be relevant to thesubject matter of other groupings.

Group A

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.05 to about 0.9 equivalents of at least one branched        polyol having 4 to 12 carbon atoms and at least 3 hydroxyl        groups; and    -   (c) about 0.1 to about 0.95 equivalents of at least one diol        having 2 to 18 carbon atoms,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol and the reaction        components are maintained at a temperature of at least about        100° C. for at least about 10 minutes.

In other non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components consisting of:

-   -   (a) about 1 equivalent of 4,4′-methylene-bis-(cyclohexyl        isocyanate);    -   (b) about 0.3 to about 0.5 equivalents of trimethylolpropane;        and    -   (c) about 0.3 to about 0.7 equivalents of 1,10-dodecanediol,        butanediol or pentanediol, wherein the reaction components are        maintained at a temperature of at least about 100° C. for at        least about 10 minutes.

In some non-limiting embodiments, the present invention provides anarticle comprising a polyurethane comprising a reaction product ofcomponents comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.1 to about 0.9 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups; and    -   (c) about 0.1 to about 0.9 equivalents of at least one diol        having 2 to 12 carbon atoms,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol, and the article has a        Gardner Impact strength of at least about 200 in-lb (23 Joules)        according to ASTM-D 5420-04.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethane comprising the step of reacting in a one potprocess components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.1 to about 0.9 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups; and    -   (c) about 0.1 to about 0.9 equivalents of at least one diol        having 2 to 12 carbon atoms,        wherein the components are essentially free of polyester polyol        and polyether polyol and the reaction components are maintained        at a temperature of at least about 100° C. for at least about 10        minutes.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethane comprising the steps of:

-   -   (a) reacting at least one polyisocyanate and at least one        branched polyol having 4 to 18 carbon atoms and at least 3        hydroxyl groups to form a polyurethane prepolymer; and    -   (b) reacting the polyurethane prepolymer with at least one diol        having 2 to 12 carbon atoms to form the polyurethane        wherein the reaction components are maintained at a temperature        of at least about 100° C. for at least about 10 minutes.        Group B

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   (a) an isocyanate functional urethane prepolymer comprising a    reaction product of components comprising:    -   (i) about 1 equivalent of at least one polyisocyanate; and    -   (ii) about 0.1 to about 0.5 equivalents of at least one diol        having 2 to 18 carbon atoms; and-   (b) about 0.05 to about 0.9 equivalents of at least one branched    polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups;    and-   (c) up to about 0.45 equivalents of at least one diol having 2 to 18    carbon atoms,    wherein the reaction product components are essentially free of    polyester polyol and polyether polyol.    Group C

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) at least one polyisocyanate selected from the group        consisting of polyisocyanate trimers and branched        polyisocyanates, the polyisocyanate having at least three        isocyanate functional groups; and    -   (b) at least one aliphatic polyol having 4 to 18 carbon atoms        and at least two hydroxyl groups,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol.

In other non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components consisting of:

-   -   (a) about 1 equivalent of 4,4′-methylene-bis-(cyclohexyl        isocyanate);    -   (b) about 1.1 equivalents of butanediol; and    -   (c) about 0.1 equivalents of isophorone diisocyanate trimer.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethane comprising the step of reacting in a one potprocess components comprising:

-   -   (a) at least one polyisocyanate trimer or branched        polyisocyanate, the polyisocyanate having at least three        isocyanate functional groups; and    -   (b) at least one aliphatic polyol having 4 to 18 carbon atoms        and at least two hydroxyl groups,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol.        Group D

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) at least one polyisocyanate;    -   (b) at least one branched polyol having 4 to 18 carbon atoms and        at least 3 hydroxyl groups; and    -   (c) at least one polyol having one or more bromine atoms, one or        more phosphorus atoms or combinations thereof.

In other non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components consisting of:

-   -   (a) about 1 equivalent of 4,4′-methylene-bis-(cyclohexyl        isocyanate);    -   (b) about 0.3 to about 0.5 equivalents of trimethylolpropane;    -   (c) about 0.2 to about 0.5 equivalents of        bis(4-(2-hydroxyethoxy)-3,5-dibromophenyl)sulfone;    -   (d) about 0.2 to about 0.5 equivalents of 1,4-cyclohexane        dimethanol; and    -   (e) about 0.2 to about 0.5 equivalents of        3,6-dithia-1,2-octanediol.

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) at least one polyisocyanate selected from the group        consisting of polyisocyanate trimers and branched        polyisocyanates, the polyisocyanate having at least three        isocyanate functional groups;    -   (b) at least one aliphatic polyol having 4 to 18 carbon atoms        and at least 2 hydroxyl groups; and    -   (c) at least one polyol having one or more bromine atoms, one or        more phosphorus atoms or combinations thereof.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethane comprising the step of reacting in a one potprocess components comprising:

-   -   (a) at least one polyisocyanate;    -   (b) at least one branched polyol having 4 to 18 carbon atoms and        at least 3 hydroxyl groups; and    -   (c) at least one polyol having one or more bromine atoms, one or        more phosphorus atoms or combinations thereof.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethane comprising the steps of:

-   -   (a) reacting at least one polyisocyanate and at least one        branched polyol having 4 to 18 carbon atoms and at least 3        hydroxyl groups to form a polyurethane prepolymer; and    -   (b) reacting the polyurethane prepolymer with at least one        polyol having one or more bromine atoms, one or more phosphorus        atoms or combinations thereof to form the polyurethane.        Group E

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.3 to about 1 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups; and    -   (c) about 0.01 to about 0.3 equivalents of at least one        polycarbonate diol,        wherein the reaction product components are essentially free of        polyether polyol and amine curing agent and wherein the reaction        components are maintained at a temperature of at least about        100° C. for at least about 10 minutes.

In other non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components consisting of:

-   -   (a) about 1 equivalent of 4,4′-methylene-bis-(cyclohexyl        isocyanate);    -   (b) about 0.3 equivalents of trimethylolpropane;    -   (c) about 0.5 to about 0.55 equivalents of butanediol or        pentanediol; and    -   (d) about 0.15 to about 0.2 equivalents of polyhexylene        carbonate diol        wherein the reaction components are maintained at a temperature        of at least about 100° C. for at least about 10 minutes.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethane comprising the step of reacting in a one potprocess components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.3 to about 1 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups; and    -   (c) about 0.01 to about 0.3 equivalents of at least one        polycarbonate diol,        wherein the reaction product components are essentially free of        polyether polyol and amine curing agent and wherein the reaction        components are maintained at a temperature of at least about        100° C. for at least about 10 minutes.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethane comprising the steps of:

-   -   (a) reacting at least one polyisocyanate and at least one        branched polyol having 4 to 18 carbon atoms and at least 3        hydroxyl groups to form a polyurethane prepolymer; and    -   (b) reacting the polyurethane prepolymer with at least one        polycarbonate diol to form the polyurethane.        Group F

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.3 to about 1 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups;    -   (c) about 0.01 to about 0.3 equivalents of at least one        polycarbonate diol; and    -   (d) about 0.1 to about 0.9 equivalents of at least one diol        having 2 to 18 carbon atoms,        wherein the reaction product components are essentially free of        polyether polyol and wherein the reaction components are        maintained at a temperature of at least about 100° C. for at        least about 10 minutes.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethane comprising the step of reacting in a one potprocess components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.3 to about 1 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups;    -   (c) about 0.01 to about 0.3 equivalents of at least one        polycarbonate diol; and    -   (d) about 0.1 to about 0.9 equivalents of at least one diol        having 2 to 18 carbon atoms,        wherein the reaction product components are essentially free of        polyether polyol and wherein the reaction components are        maintained at a temperature of at least about 100° C. for at        least about 10 minutes.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethane comprising the steps of:

-   -   (a) reacting at least one polyisocyanate and at least one        branched polyol having 4 to 18 carbon atoms and at least 3        hydroxyl groups to form a polyurethane prepolymer; and    -   (b) reacting the polyurethane prepolymer with at least one        polycarbonate diol and at least one diol having 2 to 18 carbon        atoms to form the polyurethane        wherein the reaction product components are essentially free of        polyether polyol.        Group G

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.3 to about 1 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups;    -   (c) about 0.01 to about 0.3 equivalents of at least one polyol        selected from the group consisting of polyester polyol,        polycaprolactone polyol and mixtures thereof; and    -   (d) about 0.1 to about 0.7 equivalents of at least one aliphatic        diol,        wherein the reaction product components are essentially free of        polyether polyol and amine curing agent and wherein the reaction        components are maintained at a temperature of at least about        100° C. for at least about 10 minutes.

In other non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components consisting of:

-   -   (a) about 1 equivalent of 4,4′-methylene-bis-(cyclohexyl        isocyanate);    -   (b) about 0.3 equivalents of trimethylolpropane;    -   (c) about 0.5 equivalents of decanediol; and    -   (d) about 0.2 equivalents of polycaprolactone polyol,        wherein the reaction components are maintained at a temperature        of at least about 100° C. for at least about 10 minutes.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethane comprising the step of reacting in a one potprocess components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.3 to about 1 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups; and    -   (c) about 0.01 to about 0.3 equivalents of at least one polyol        selected from the group consisting of polyester polyol,        polycaprolactone polyol and mixtures thereof; and    -   (d) about 0.1 to about 0.7 equivalents of at least one aliphatic        diol,        wherein the reaction product components are essentially free of        polyether polyol and amine curing agent.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethane comprising the steps of:

(a) reacting at least one polyisocyanate and at least one branchedpolyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups toform a polyurethane prepolymer; and

-   -   (b) reacting the polyurethane prepolymer with at least one        polyol selected from the group consisting of polyester polyol,        polycaprolactone polyol and mixtures thereof and about 0.1 to        about 0.7 equivalents of at least one aliphatic diol to form the        polyurethane.        Group H

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) a prepolymer which is the reaction product of components        comprising:        -   (1) at least one polyisocyanate;        -   (2) at least one polycaprolactone polyol; and        -   (3) at least one polyol selected from the group consisting            of polyalkylene polyol, polyether polyol and mixtures            thereof; and    -   (b) at least one diol having 2 to 18 carbon atoms.

In other non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) a prepolymer which is the reaction product of components        comprising:        -   (1) aliphatic or cycloaliphatic diisocyanate;        -   (2) polycaprolactone diol;        -   (3) polyethylene glycol; and        -   (4) polyoxyethylene and polyoxypropylene copolymer; and    -   (b) at least one diol having 2 to 18 carbon atoms.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethane comprising the steps of:

-   -   (a) reacting components comprising:        -   1) at least one polyisocyanate;        -   2) at least one polycaprolactone polyol; and        -   3) at least one polyol selected from the group consisting of            polyalkylene polyol, polyether polyol and mixtures thereof,            to form a polyurethane prepolymer; and    -   (b) reacting the prepolymer with at least one diol having 2 to        18 carbon atoms to form the polyurethane.        Group I

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s comprising a reaction product of componentscomprising:

(a) at least one isocyanate functional urea prepolymer comprising areaction product of:

-   -   (1) at least one polyisocyanate; and    -   (2) water; and

(b) at least one branched polyol having 4 to 18 carbon atoms and atleast 3 hydroxyl groups,

wherein the reaction product components are essentially free of aminecuring agent.

In some non-limiting embodiments, the present invention provides methodsof preparing poly(ureaurethane) comprising the steps of:

-   -   (a) reacting at least one polyisocyanate and water to form an        isocyanate functional urea prepolymer; and    -   (b) reacting reaction product components comprising the        isocyanate functional urea prepolymer with at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups,        wherein the reaction product components are essentially free of        amine curing agent.        Group J

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s comprising a reaction product of componentscomprising:

-   -   (a) at least one isocyanate functional urea prepolymer        comprising a reaction product of:        -   (1) at least one polyisocyanate selected from the group            consisting of polyisocyanate trimers and branched            polyisocyanates, the polyisocyanate having at least three            isocyanate functional groups; and        -   (2) water; and    -   (b) at least one aliphatic polyol having 4 to 18 carbon atoms        and at least 2 hydroxyl groups.

In some non-limiting embodiments, the present invention provides methodsof preparing poly(ureaurethane) comprising the steps of:

-   -   (a) reacting at least one polyisocyanate selected from the group        consisting of polyisocyanate trimers and branched        polyisocyanates and water to form an isocyanate functional urea        prepolymer; and    -   (b) reacting reaction product components comprising the        isocyanate functional urea prepolymer with at least one        aliphatic polyol having 4 to 18 carbon atoms and at least 2        hydroxyl groups,        wherein the reaction product components are essentially free of        amine curing agent.        Group K

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s comprising a reaction product of componentscomprising:

(a) at least one isocyanate functional ureaurethane prepolymercomprising the reaction product of:

-   -   (1) at least one isocyanate functional urethane prepolymer        comprising the reaction product of:        -   (i) a first amount of at least one polyisocyanate; and        -   (ii) a first amount of at least one branched polyol; and    -   (2) water, to form an isocyanate functional ureaurethane        prepolymer; and

(b) a second amount of at least one polyisocyanate and a second amountof at least one branched polyol.

In some non-limiting embodiments, the present invention provides methodsof preparing poly(ureaurethane) comprising the steps of:

(a) reacting at least one polyisocyanate and at least one branchedpolyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups toform an isocyanate functional urethane prepolymer;

(b) reacting the isocyanate functional urethane prepolymer with waterand polyisocyanate to form an isocyanate functional ureaurethaneprepolymer; and

(c) reacting reaction product components comprising the isocyanatefunctional ureaurethane prepolymer with at least one aliphatic polyolhaving 4 to 18 carbon atoms and at least 2 hydroxyl groups,

wherein the reaction product components are essentially free of aminecuring agent.

Group L

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s comprising a reaction product of componentscomprising:

-   -   (a) at least one isocyanate functional ureaurethane prepolymer        comprising the reaction product of:        -   (1) at least one isocyanate functional urethane prepolymer            comprising the reaction product of:            -   (i) a first amount of at least one polyisocyanate                selected from the group consisting of polyisocyanate                trimers and branched polyisocyanates, the polyisocyanate                having at least three isocyanate functional groups; and            -   (ii) a first amount of at least one aliphatic polyol;                and        -   (2) water, to form an isocyanate functional ureaurethane            prepolymer; and    -   (b) a second amount of at least one polyisocyanate and a second        amount of at least one aliphatic polyol.

In some non-limiting embodiments, the present invention provides methodsof preparing poly(ureaurethane) comprising the steps of:

(a) reacting at least one polyisocyanate selected from the groupconsisting of polyisocyanate trimers and branched polyisocyanates and atleast one aliphatic polyol having 4 to 18 carbon atoms and at least 2hydroxyl groups to form an isocyanate functional urethane prepolymer;

(b) reacting the isocyanate functional urethane prepolymer with waterand polyisocyanate to form an isocyanate functional ureaurethaneprepolymer; and

(c) reacting reaction product components comprising the isocyanatefunctional ureaurethane prepolymer with at least one aliphatic polyolhaving 4 to 18 carbon atoms and at least 2 hydroxyl groups,

wherein the reaction product components are essentially free of aminecuring agent.

Group M

In other non-limiting embodiments, the present invention providespoly(ureaurethane)s comprising a reaction product of componentscomprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.1 to about 0.9 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups;    -   (c) about 0.1 to about 0.9 equivalents of at least one aliphatic        diol having 2 to 18 carbon atoms; and    -   (d) at least one amine curing agent,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol.

In other non-limiting embodiments, the present invention providesmethods of preparing poly(ureaurethane) comprising the step of reactingin a one pot process components comprising:

-   -   (a) at least one polyisocyanate;    -   (b) at least one branched polyol having 4 to 18 carbon atoms and        at least 3 hydroxyl groups;    -   (c) at least one aliphatic diol having 2 to 18 carbon atoms; and    -   (d) amine curing agent,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol.        Group N

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s comprising a reaction product of componentscomprising:

-   -   (a) at least one polyisocyanate selected from the group        consisting of polyisocyanate trimers and branched        polyisocyanates, the polyisocyanate having at least three        isocyanate functional groups;    -   (b) about 0.1 to about 0.9 equivalents of at least one polyol        having 4 to 18 carbon atoms and at least 2 hydroxyl groups; and    -   (c) at least one amine curing agent,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol.

In some non-limiting embodiments, the present invention provides methodsof preparing poly(ureaurethane) comprising the step of reacting in a onepot process components comprising:

-   -   (a) at least one polyisocyanate selected from the group        consisting of polyisocyanate trimers and branched        polyisocyanates;    -   (b) at least one aliphatic polyol having 4 to 18 carbon atoms        and at least 3 hydroxyl groups;    -   (c) at least one aliphatic diol having 2 to 18 carbon atoms; and    -   (d) amine curing agent,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol.        Group O

In some non-limiting embodiments, the present invention providespolyurethane materials comprising a first portion of crystallineparticles having self-orientation and bonded together to fix theirorientation along a first crystallographic direction and a secondportion of crystalline particles having self-orientation and bondedtogether to fix their orientation along a second crystallographicdirection, the first crystallographic direction being different from thesecond crystallographic direction, wherein said crystalline particlescomprise at least about 30% of the total volume of the polyurethanematerial.

Group P

In some non-limiting embodiments, the present invention provides methodsof preparing a polyurethane powder coating composition comprising thesteps of: reacting at least one polyisocyanate with at least onealiphatic polyol to form a generally solid, hydroxy functionalprepolymer; melting the hydroxy functional prepolymer; melting at leastone generally solid polyisocyanate to form a melted polyisocyanate;mixing the hydroxy functional prepolymer and melted polyisocyanate toform a mixture; and solidifying the mixture to form a generally solidpowder coating composition.

In other non-limiting embodiments, the present invention providesmethods of preparing a polyurethane powder coating compositioncomprising the steps of: reacting at least one polyisocyanate with atleast one aliphatic polyol to form a generally solid, hydroxy functionalprepolymer; dissolving the hydroxy functional prepolymer in a firstsolvent to form a first solution; dissolving at least one generallysolid polyisocyanate in a second solvent that is the same as orcompatible with the first solvent to form a second solution; mixing thefirst and second solutions; and removing substantially all of thesolvent to form a generally solid powder coating composition.

Group Q

In some non-limiting embodiments, the present invention providespolyurethane compositions comprising: at least one polyurethanecomprising a reaction product of components comprising:

(a) (i) at least one polyisocyanate;

-   -   (ii) at least one branched polyol having 4 to 18 carbon atoms        and at least 3 hydroxyl groups; and    -   (iii) at least one diol having 2 to 18 carbon atoms; and

(b) at least one reinforcement material selected from the groupconsisting of polymeric inorganic materials, nonpolymeric inorganicmaterials, polymeric organic materials, nonpolymeric organic materials,composites thereof, and combinations thereof.

In other non-limiting embodiments, the present invention providespolyurethane compositions comprising:

(a) at least one polyurethane comprising a reaction product ofcomponents comprising:

-   -   (i) at least one polyisocyanate;    -   (ii) at least one branched polyol having 4 to 18 carbon atoms        and at least 3 hydroxyl groups; and    -   (iii) at least one polyol having one or more bromine atoms, one        or more phosphorus atoms or combinations thereof; and

(b) at least one reinforcement material selected from the groupconsisting of polymeric inorganic materials, nonpolymeric inorganicmaterials, polymeric organic materials, nonpolymeric organic materials,composites thereof, and mixtures thereof.

In other non-limiting embodiments, the present invention providespolyurethane compositions comprising:

(a) a polyurethane comprising a reaction product of componentscomprising:

-   -   (i) a prepolymer which is the reaction product of components        comprising:        -   (1) at least one polyisocyanate;        -   (2) at least one polycaprolactone polyol; and        -   (3) at least one polyol selected from the group consisting            of polyalkylene polyol, polyether polyol and mixtures            thereof; and    -   (ii) at least one diol having 2 to 18 carbon atoms; and

(b) at least one reinforcement material selected from the groupconsisting of polymeric inorganic materials, nonpolymeric inorganicmaterials, polymeric organic materials, nonpolymeric organic materials,composites thereof, and mixtures thereof.

In other non-limiting embodiments, the present invention providespolyurethane compositions comprising:

(a) at least one polyurethane comprising a reaction product ofcomponents comprising:

-   -   (i) at least one polyisocyanate selected from the group        consisting of polyisocyanate trimers or branched        polyisocyanates, the polyisocyanate having at least three        isocyanate functional groups; and    -   (ii) at least one aliphatic polyol having 4 to 18 carbon atoms        and at least two hydroxyl groups; and

(b) at least one reinforcement material selected from the groupconsisting of polymeric inorganic materials, nonpolymeric inorganicmaterials, polymeric organic materials, nonpolymeric organic materials,composites thereof, and mixtures thereof.

In other non-limiting embodiments, the present invention providespoly(ureaurethane)s composition comprising:

(a) at least one poly(ureaurethane) comprising a reaction product ofcomponents comprising:

-   -   (i) at least one isocyanate functional prepolymer comprising a        reaction product of:        -   1. at least one polyisocyanate; and        -   2. water; and    -   (ii) at least one branched polyol having 4 to 18 carbon atoms        and at least 3 hydroxyl groups,        wherein the reaction product components are essentially free of        amine curing agent; and

(b) at least one reinforcement material selected from the groupconsisting of polymeric inorganic materials, nonpolymeric inorganicmaterials, polymeric organic materials, nonpolymeric organic materials,composites thereof, and mixtures thereof.

In other non-limiting embodiments, the present invention providespoly(ureaurethane)s composition comprising:

(a) at least one poly(ureaurethane) comprising a reaction product ofcomponents comprising:

-   -   (i) at least one isocyanate functional urethane prepolymer        comprising a reaction product of:        -   1. a first amount of at least one polyisocyanate; and        -   2. a first amount of at least one branched polyol; and

(ii) water, to form an isocyanate functional ureaurethane prepolymer;and

(b) a second amount of at least one polyisocyanate and a second amountof at least one branched polyol; and

(c) at least one reinforcement material selected from the groupconsisting of polymeric inorganic materials, nonpolymeric inorganicmaterials, polymeric organic materials, nonpolymeric organic materials,composites thereof, and mixtures thereof.

In some non-limiting embodiments, the present invention provides methodsfor forming a reinforced polyurethane composition, comprising the stepsof: mixing a precursor solution of the reaction product components ofthe above polyurethane or poly(ureaurethane) with a precursor for thenanostructures; forming the nanostructures from the precursor of thenanostructures in the polyurethane matrix; and polymerizing theprecursor of the reaction product components to form the polyurethane.

Group R

In some non-limiting embodiments, the present invention provides alaminate comprising:

(a) at least one layer of at least one polyurethane comprising areaction product of components comprising:

-   -   (i) at least one polyisocyanate;    -   (ii) at least one branched polyol having 4 to 18 carbon atoms        and at least 3 hydroxyl groups; and    -   (iii) at least one diol having 2 to 18 carbon atoms; and

(b) at least one layer of a substrate selected from the group consistingof paper, glass, ceramic, wood, masonry, textile, metal or organicpolymeric material and combinations thereof.

In other non-limiting embodiments, the present invention provides alaminate comprising:

(a) at least one layer of at least one polyurethane comprising areaction product of components comprising:

-   -   (i) at least one polyisocyanate;    -   (ii) at least one branched polyol having 4 to 18 carbon atoms        and at least 3 hydroxyl groups; and    -   (iii) at least one polyol having one or more bromine atoms, one        or more phosphorus atoms or combinations thereof; and

(b) at least one layer of a substrate selected from the group consistingof paper, glass, ceramic, wood, masonry, textile, metal or organicpolymeric material and combinations thereof.

In other non-limiting embodiments, the present invention provides alaminate comprising:

(a) at least one layer of at least one polyurethane comprising areaction product of components comprising:

-   -   (i) a prepolymer which is the reaction product of components        comprising:        -   (1) at least one polyisocyanate;        -   (2) at least one polycaprolactone polyol; and        -   (3) at least one polyol selected from the group consisting            of polyalkylene polyol, polyether polyol and mixtures            thereof; and    -   (ii) at least one diol having 2 to 18 carbon atoms; and

(b) at least one layer of a substrate selected from the group consistingof paper, glass, ceramic, wood, masonry, textile, metal or organicpolymeric material and combinations thereof.

In other non-limiting embodiments, the present invention provides alaminate comprising:

(a) at least one layer of at least one polyurethane comprising areaction product of components comprising:

-   -   (i) at least one polyisocyanate selected from the group        consisting of polyisocyanate trimers or branched        polyisocyanates, the polyisocyanate having at least three        isocyanate functional groups; and    -   (ii) at least one aliphatic polyol having 4 to 18 carbon atoms        and at least two hydroxyl groups; and

(b) at least one layer of a substrate selected from the group consistingof paper, glass, ceramic, wood, masonry, textile, metal or organicpolymeric material and combinations thereof.

In other non-limiting embodiments, the present invention provides alaminate comprising:

(a) at least one layer of at least one poly(ureaurethane) comprising areaction product of components comprising:

-   -   (i) at least one isocyanate functional prepolymer comprising a        reaction product of:        -   1. at least one polyisocyanate; and        -   2. water; and    -   (ii) at least one branched polyol having 4 to 18 carbon atoms        and at least 3 hydroxyl groups,        wherein the reaction product components are essentially free of        amine curing agent; and

(b) at least one layer of a substrate selected from the group consistingof paper, glass, ceramic, wood, masonry, textile, metal or organicpolymeric material and combinations thereof.

In other non-limiting embodiments, the present invention provides alaminate comprising:

(A) at least one layer of at least one poly(ureaurethane) comprising areaction product of components comprising:

-   -   (a) at least one isocyanate functional ureaurethane prepolymer        comprising a reaction product of components comprising        -   (1) at least one isocyanate functional urethane prepolymer            comprising a reaction product of:            -   a. a first amount of at least one polyisocyanate; and            -   b. a first amount of at least one branched polyol;

and

-   -   -   (2) water, to form an isocyanate functional ureaurethane            prepolymer; and

    -   (b) a second amount of at least one polyisocyanate and a second        amount of at least one branched polyol; and

(B) at least one layer of a substrate selected from the group consistingof paper, glass, ceramic, wood, masonry, textile, metal or organicpolymeric material and combinations thereof.

Cured compositions, articles, laminates and methods of making and usingthe same comprising the above polyurethanes and poly(ureaurethane)s arealso provided by the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing summary, as well as the following detailed description,will be better understood when read in conjunction with the appendeddrawings. In the drawings:

FIG. 1 is a graph of G′ and G″ as a function of temperature measuredusing Dynamic Mechanical Analysis (DMA) showing storage modulus, lossmodulus and tan Delta for a casting of a polyurethane according toExample A, Formulation 1 of the present invention;

FIG. 2 is a graph of G′ and G″ as a function of temperature measuredusing Dynamic Mechanical Analysis (DMA) showing storage modulus, lossmodulus and tan Delta for a casting of a polyurethane according toExample A, Formulation 2 of the present invention;

FIG. 3 is a graph of G′ and G″ as a function of temperature measuredusing Dynamic Mechanical Analysis (DMA) showing storage modulus, lossmodulus and tan Delta for a casting of a polyurethane according toExample A, Formulation 40 of the present invention;

FIG. 4 is a TEM photomicrograph showing a casting of a polyurethaneaccording to Example A, Formulation 2 analyzed two weeks after formationaccording to the present invention;

FIG. 5 is a TEM photomicrograph showing a casting of a polyurethaneaccording to Example A, Formulation 2 analyzed about three weeks afterformation according to the present invention;

FIG. 6 is a TEM photomicrograph showing a first portion of a casting ofa polyurethane according to Example A, Formulation 2 analyzed aboutseven months after formation according to the present invention;

FIG. 7 is an electron diffraction pattern of a casting of thepolyurethane of Example A, Formulation 2 of FIG. 6;

FIG. 8 is a TEM photomicrograph showing a second portion of the castingof the polyurethane of FIG. 6 according to Example A, Formulation 2prepared after aging at ambient conditions for about seven monthsaccording to the present invention;

FIG. 9 is a TEM photomicrograph showing a first portion of a casting ofa polyurethane according to Example A, Formulation 2 prepared afteraging at ambient temperature for about two to four weeks;

FIG. 10 is a TEM photomicrograph showing a second portion of the castingof the polyurethane according to Example A, Formulation 2 shown in FIG.9;

FIG. 11 is a TEM photomicrograph showing a casting of a polyurethaneaccording to Example A, Formulation 2;

FIG. 12 is a TEM photomicrograph showing a first portion of a casting ofa polyurethane according to Example A, Formulation 2 prepared afteraging at ambient temperature for about seven months;

FIG. 13 is a TEM photomicrograph showing a second portion of a castingof a polyurethane according to Example A, Formulation 2 shown in FIG.12;

FIG. 14 is a graph of heat flow as a function of temperature measuredusing Differential Scanning Calorimetry (DSC) for castings of apolyurethane according to Example A, Formulation 2 measured after agingat ambient conditions for two weeks, three months and seven months,respectively, according to the present invention;

FIG. 15 is a graph of Gardner Impact as a function of Young's Modulusfor castings of a polyurethane according to Example A, Formulations 1and 2 measured after aging at ambient conditions for seven months andone year, respectively, according to the present invention;

FIG. 16 is a graph of storage modulus, loss modulus and tan delta as afunction of temperature measured using DMA for a casting of apolyurethane prepared according to Example A, Formulation 114, accordingto the present invention;

FIG. 17 is a photograph of a perspective view of a test sample ofFormulation 2, Example A after shooting of the sample with 0.40 caliberbullets from 30 feet (9.2 m) at a velocity of 987 ft/sec (300.8 m/sec);

FIG. 18 is a photograph of a front elevational view of a test sample ofFormulation 2, Example A after shooting of the sample with a 12 gaugeshotgun shot from 20 feet (6.1 m) at a velocity of 1290 ft/sec (393.2m/sec) using heavy game lead shot pellets;

FIG. 19 is a photograph of a front elevational view of a test sample ofFormulation 93, Example A is a photograph of a front elevational view ofa test sample of 9 mm bullets shot from 20 feet (6.1 m) at a velocity of1350 ft/sec (411.5 m/sec);

FIG. 20 is a photograph of a perspective view of a test sample ofFormulation 94, Example A after shooting of the sample with a 9 mmbullet shot from 20 feet (6.1 m) at an initial velocity of 1350 ft/sec(411.5 m/sec);

FIG. 21 is a side elevational view of the sample shown in FIG. 20;

FIG. 22 is front elevational view of a portion of a composite accordingto the present invention after shooting of the sample with four 7.62×39mm bullets having a steel core shot from an AK-47 rifle from a distanceof 30 yards (27.4 m) at an initial velocity of 2700 ft/sec (823 m/sec);

FIG. 23 is a rear perspective view of the sample of FIG. 22.

FIG. 24 is a graph of heat flow as a function of temperature measuredusing Differential Scanning Calorimetry (DSC) for a casting of apolyurethane prepared according to Example A, Formulation 2 of thepresent invention;

FIG. 25 is a graph of heat flow as a function of temperature measuredusing (DSC) for a casting of a polyurethane prepared according toExample A, Formulation 136 of the present invention; and

FIG. 26 is a graph of weight loss as a function of temperature measuredusing Thermogravimetric Analysis (TGA) for a casting of a polyurethaneprepared according to Example A, Formulation 136 of the presentinvention.

DETAILED DESCRIPTION

As used herein, spatial or directional terms, such as “inner”, “left”,“right”, “up”, “down”, “horizontal”, “vertical” and the like, relate tothe invention as it is described herein. However, it is to be understoodthat the invention can assume various alternative orientations and,accordingly, such terms are not to be considered as limiting. For thepurposes of this specification, unless otherwise indicated, all numbersexpressing quantities of ingredients, reaction conditions, dimensions,physical characteristics, and so forth used in the specification andclaims are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include any and all sub-ranges betweenand including the recited minimum value of 1 and the recited maximumvalue of 10, that is, all subranges beginning with a minimum value equalto or greater than 1 and ending with a maximum value equal to or lessthan 10, and all subranges in between, e.g., 1 to 6.3, or 5.5 to 10, or2.7 to 6.1.

“Alkyl” means an aliphatic hydrocarbon group which may be straight orbranched and comprising about 1 to about 20 carbon atoms in the chain.Non-limiting examples of suitable alkyl groups contain about 1 to about18 carbon atoms in the chain, or about 1 to about 6 carbon atoms in thechain. Branched means that one or more lower alkyl groups such asmethyl, ethyl or propyl, are attached to a linear alkyl chain. “Loweralkyl” or “short chain alkyl” means a group having about 1 to about 6carbon atoms in the chain which may be straight or branched. “Alkyl” maybe unsubstituted or optionally substituted by one or more substituentswhich may be the same or different, each substituent being independentlyselected from the group consisting of halo, alkyl, aryl, cycloalkyl,cyano, hydroxy, alkoxy, alkylthio, amino, —NH(cycloalkyl), —N(alkyl)₂,carboxy and —C(O)O-alkyl. Non-limiting examples of suitable alkyl groupsinclude methyl, ethyl, n-propyl, isopropyl and t-butyl.

“Alkylene” means a difunctional group obtained by removal of a hydrogenatom from an alkyl group that is defined above. Non-limiting examples ofalkylene include methylene, ethylene and propylene.

“Aryl” means an aromatic monocyclic or multicyclic ring systemcomprising about 6 to about 14 carbon atoms, or about 6 to about 10carbon atoms. The aryl group can be optionally substituted with one ormore “ring system substituents” which may be the same or different, andare as defined herein. Non-limiting examples of suitable aryl groupsinclude phenyl and naphthyl.

“Heteroaryl” means an aromatic monocyclic or multicyclic ring systemcomprising about 5 to about 14 ring atoms, or about 5 to about 10 ringatoms, in which one or more of the ring atoms is an element other thancarbon, for example nitrogen, oxygen or sulfur, alone or in combination.In some non-limiting embodiments, the heteroaryls contain about 5 toabout 6 ring atoms. The “heteroaryl” can be optionally substituted byone or more “ring system substituents” which may be the same ordifferent, and are as defined herein. The prefix aza, oxa or thia beforethe heteroaryl root name means that at least one of a nitrogen, oxygenor sulfur atom respectively, is present as a ring atom. A nitrogen atomof a heteroaryl can be optionally oxidized to the corresponding N-oxide.Non-limiting examples of suitable heteroaryls include pyridyl,pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone (includingN-substituted pyridones), isoxazolyl, isothiazolyl, oxazolyl, thiazolyl,pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl,1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, phthalazinyl,oxindolyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl,benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothienyl,quinolinyl, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidyl,pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindolyl,1,2,4-triazinyl, benzothiazolyl and the like. The term “heteroaryl” alsorefers to partially saturated heteroaryl moieties such as, for example,tetrahydroisoquinolyl, tetrahydroquinolyl and the like.

“Aralkyl” or “arylalkyl” means an aryl-alkyl- group in which the aryland alkyl are as previously described. In some non-limiting embodiments,the aralkyls comprise a lower alkyl group. Non-limiting examples ofsuitable aralkyl groups include benzyl, 2-phenethyl andnaphthalenylmethyl. The bond to the parent moiety is through the alkyl.

“Alkylaryl” means an alkyl-aryl- group in which the alkyl and aryl areas previously described. In some non-limiting embodiments, thealkylaryls comprise a lower alkyl group. A non-limiting example of asuitable alkylaryl group is tolyl. The bond to the parent moiety isthrough the aryl.

“Cycloalkyl” means a non-aromatic mono- or multicyclic ring systemcomprising about 3 to about 10 carbon atoms, or about 5 to about 10carbon atoms. In some non-limiting embodiments, the cycloalkyl ringcontains about 5 to about 7 ring atoms. The cycloalkyl can be optionallysubstituted with one or more “ring system substituents” which may be thesame or different, and are as defined above. Non-limiting examples ofsuitable monocyclic cycloalkyls include cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl and the like. Non-limiting examples of suitablemulticyclic cycloalkyls include 1-decalinyl, norbornyl, adamantyl andthe like.

“Halogen” or “halo” means fluorine, chlorine, bromine, or iodine. Insome non-limiting embodiments, the halogen groups are fluorine, chlorineor bromine.

“Ring system substituent” means a substituent attached to an aromatic ornon-aromatic ring system which, for example, replaces an availablehydrogen on the ring system. Ring system substituents may be the same ordifferent, each being independently selected from the group consistingof alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, alkylaryl,heteroaralkyl, heteroarylalkenyl, heteroarylalkynyl, alkylheteroaryl,hydroxy, hydroxyalkyl, alkoxy, aryloxy, aralkoxy, acyl, aroyl, halo,nitro, cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl,aralkoxycarbonyl, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl,alkylthio, arylthio, heteroarylthio, aralkylthio, heteroaralkylthio,cycloalkyl, heterocyclyl, —C(═N—CN)—NH₂, —C(═NH)—NH₂, —C(═NH)—NH(alkyl),Y₁Y₂N—, Y₁Y₂N-alkyl-, Y₁Y₂NC(O)—, Y₁Y₂NSO₂— and —SO₂NY₁Y₂, wherein Y₁and Y₂ can be the same or different and are independently selected fromthe group consisting of hydrogen, alkyl, aryl, cycloalkyl, and aralkyl.“Ring system substituent” may also mean a single moiety whichsimultaneously replaces two available hydrogens on two adjacent carbonatoms (one H on each carbon) on a ring system. Examples of such moietiesare methylene dioxy, ethylenedioxy, —C(CH₃)₂— and the like which formmoieties such as, for example:

“Heterocyclyl” means a non-aromatic saturated monocyclic or multicyclicring system comprising about 3 to about 10 ring atoms, or about 5 toabout 10 ring atoms, in which one or more of the atoms in the ringsystem is an element other than carbon, for example nitrogen, oxygen orsulfur, alone or in combination. There are no adjacent oxygen and/orsulfur atoms present in the ring system. In some non-limitingembodiments, the heterocyclyl contains about 5 to about 6 ring atoms.The prefix aza, oxa or thia before the heterocyclyl root name means thatat least a nitrogen, oxygen or sulfur atom respectively is present as aring atom. Any —NH in a heterocyclyl ring may exist protected such as,for example, as an —N(Boc), —N(CBz), —N(Tos) group and the like; suchprotections are also considered part of this invention. The heterocyclylcan be optionally substituted by one or more “ring system substituents”which may be the same or different, and are as defined herein. Thenitrogen or sulfur atom of the heterocyclyl can be optionally oxidizedto the corresponding N-oxide, S-oxide or S,S-dioxide. Non-limitingexamples of suitable monocyclic heterocyclyl rings include piperidyl,pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl,1,4-dioxanyl, tetrahydrofuranyl, tetrahydrothiophenyl, lactam, lactone,and the like.

It should be noted that in hetero-atom containing ring systems of thisinvention, there are no hydroxyl groups on carbon atoms adjacent to a N,O or S, as well as there are no N or S groups on carbon adjacent toanother heteroatom. Thus, for example, in the ring:

there is no —OH attached directly to carbons marked 2 and 5.

It should also be noted that tautomeric forms such as, for example, themoieties:

are considered equivalent in certain embodiments of this invention.

“Heteroaralkyl” means a heteroaryl-alkyl- group in which the heteroaryland alkyl are as previously described. In some non-limiting embodiments,the heteroaralkyl contains a lower alkyl group. Non-limiting examples ofsuitable heteroaralkyl groups include pyridylmethyl, andquinolin-3-ylmethyl. The bond to the parent moiety is through the alkyl.

“Hydroxyalkyl” means a HO-alkyl- group in which alkyl is as previouslydefined. In some non-limiting embodiments, the hydroxyalkyl contains alower alkyl group. Non-limiting examples of suitable hydroxyalkyl groupsinclude hydroxymethyl and 2-hydroxyethyl.

“Alkoxy” means an alkyl-O— group in which the alkyl group is aspreviously described. Non-limiting examples of suitable alkoxy groupsinclude methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. The bond tothe parent moiety is through the ether oxygen.

“Aryloxy” means an aryl-O— group in which the aryl group is aspreviously described. Non-limiting examples of suitable aryloxy groupsinclude phenoxy and naphthoxy. The bond to the parent moiety is throughthe ether oxygen.

“Alkylthio” means an alkyl-S— group in which the alkyl group is aspreviously described. Non-limiting examples of suitable alkylthio groupsinclude methylthio and ethylthio. The bond to the parent moiety isthrough the sulfur.

“Arylthio” means an aryl-S— group in which the aryl group is aspreviously described. Non-limiting examples of suitable arylthio groupsinclude phenylthio and naphthylthio. The bond to the parent moiety isthrough the sulfur.

“Aralkylthio” means an aralkyl-S— group in which the aralkyl group is aspreviously described. Non-limiting example of a suitable aralkylthiogroup is benzylthio. The bond to the parent moiety is through thesulfur.

“Alkoxycarbonyl” means an alkyl-O—CO— group. Non-limiting examples ofsuitable alkoxycarbonyl groups include methoxycarbonyl andethoxycarbonyl. The bond to the parent moiety is through the carbonyl.

“Aryloxycarbonyl” means an aryl-O—C(O)— group. Non-limiting examples ofsuitable aryloxycarbonyl groups include phenoxycarbonyl andnaphthoxycarbonyl. The bond to the parent moiety is through thecarbonyl.

“Aralkoxycarbonyl” means an aralkyl-O—C(O)— group. A non-limitingexample of a suitable aralkoxycarbonyl group is benzyloxycarbonyl. Thebond to the parent moiety is through the carbonyl.

“Alkylsulfonyl” means an alkyl-S(O₂)— group. In some non-limitingembodiments, the alkylsulfonyl group includes a lower alkyl group. Thebond to the parent moiety is through the sulfonyl.

“Arylsulfonyl” means an aryl-S(O₂)— group. The bond to the parent moietyis through the sulfonyl.

The term “substituted” means that one or more hydrogens on thedesignated atom is replaced with a selection from the indicated group,provided that the designated atom's normal valency under the existingcircumstances is not exceeded, and that the substitution results in astable compound. Combinations of substituents and/or variables arepermissible only if such combinations result in stable compounds.

The term “optionally substituted” means optional substitution with thespecified groups, radicals or moieties.

It should also be noted that any carbon as well as heteroatom withunsatisfied valences in the text, schemes, examples and Tables herein isassumed to have the sufficient number of hydrogen atom(s) to satisfy thevalences.

When a functional group in a compound is termed “protected”, this meansthat the group is in modified form to preclude undesired side reactionsat the protected site when the compound is subjected to a reaction.Suitable protecting groups will be recognized by those with ordinaryskill in the art as well as by reference to standard textbooks such as,for example, T. W. Greene et al, Protective Groups in organic Synthesis(1991), Wiley, N.Y.

When any variable (e.g., aryl, heterocycle, R², etc.) occurs more thanone time in any constituent, its definition on each occurrence isindependent of its definition at every other occurrence.

As used herein, the term “composition” is intended to encompass aproduct comprising the specified ingredients in the specified amounts,as well as any product which results, directly or indirectly, fromcombination of the specified ingredients in the specified amounts.

As used herein, “formed from” or “prepared from” denotes open, e.g.,“comprising,” claim language. As such, it is intended that a composition“formed from” or “prepared from” a list of recited components be acomposition comprising at least these recited components or the reactionproduct of at least these recited components, and can further compriseother, non-recited components, during the composition's formation orpreparation. As used herein, the phrase “reaction product of” meanschemical reaction product(s) of the recited components, and can includepartial reaction products as well as fully reacted products.

As used herein, the term “polymer” in meant to encompass oligomers, andincludes without limitation both homopolymers and copolymers. The term“prepolymer” means a compound, monomer or oligomer used to prepare apolymer, and includes without limitation both homopolymer and copolymeroligomers.

The phrase “thermoplastic polymer” means a polymer that undergoes liquidflow upon heating and can be soluble in solvents.

The phrase “thermoset polymer” means a polymer that solidifies or “sets”irreversibly upon curing or crosslinking. Once cured, a crosslinkedthermoset polymer will not melt upon the application of heat and isgenerally insoluble in solvents.

As used herein, the term “cure” as used in connection with acomposition, e.g., “composition when cured” or a “cured composition”,shall mean that any curable or crosslinkable components of thecomposition are at least partially cured or crosslinked. In somenon-limiting embodiments of the present invention, the crosslink densityof the crosslinkable components, i.e., the degree of crosslinking,ranges from about 5% to about 100% of complete crosslinking. In othernon-limiting embodiments, the crosslink density ranges from about 35% toabout 85% of full crosslinking. In other non-limiting embodiments, thecrosslink density ranges from about 50% to about 85% of fullcrosslinking. One skilled in the art will understand that the presenceand degree of crosslinking, i.e., the crosslink density, can bedetermined by a variety of methods, such as dynamic mechanical thermalanalysis (DMA) using a TA Instruments DMA 2980 DMA analyzer over atemperature range of −65° F. (−18° C.) to 350° F. (177° C.) conductedunder nitrogen according to ASTM D 4065-01. This method determines theglass transition temperature and crosslink density of free films ofcoatings or polymers. These physical properties of a cured material arerelated to the structure of the crosslinked network. In an embodiment ofthe present invention, the sufficiency of cure is evaluated relative tothe solvent resistance of a cured film of the polymer. For example,solvent resistance can be measured by determining the number of doubleacetone rubs. For purposes of the present invention, a coating is deemedto be “cured” when the film can withstand a minimum of 100 doubleacetone rubs without substantial softening of the film and no removal ofthe film.

Curing of a polymerizable composition can be obtained by subjecting thecomposition to curing conditions, such as but not limited to thermalcuring, irradiation, etc., leading to the reaction of reactive groups ofthe composition and resulting in polymerization and formation of a solidpolymerizate. When a polymerizable composition is subjected to curingconditions, following polymerization and after reaction of most of thereactive groups occurs, the rate of reaction of the remaining unreactedreactive groups becomes progressively slower. In some non-limitingembodiments, the polymerizable composition can be subjected to curingconditions until it is at least partially cured. The term “at leastpartially cured” means subjecting the polymerizable composition tocuring conditions, wherein reaction of at least a portion of thereactive groups of the composition occurs, to form a solid polymerizate.The at least partially cured polymerizate can be demolded and, forexample, used to prepare articles such as windows, cut into test piecesor subjected to machining operations, such as optical lens processing.In some non-limiting embodiments, the polymerizable composition can besubjected to curing conditions such that a substantially complete cureis attained and wherein further exposure to curing conditions results inno significant further improvement in polymer properties, such asstrength or hardness.

The term “polyurethane” is intended to include not only polyurethanesthat are formed from the reaction of polyisocyanates and polyols butalso poly(ureaurethane)(s) that are prepared from the reaction ofpolyisocyanates with polyols and water and/or polyamines.

The polyurethanes and poly(ureaurethane)s of the present invention canbe useful in applications in which one or more of the followingproperties are desired: transparency, high optical quality, high Abbenumber, low color, energy-absorption, stiffness, moisture stability,ultraviolet light stability, weathering resistance, low waterabsorption, hydrolytic stability and bullet or explosive resistance.

In some embodiments, cured articles prepared from the polyurethanes andpoly(ureaurethane)s of the present invention are generally clear, canhave a luminous transmittance of at least about 80 percent, less thanabout 2 percent haze and show no visual change after 1,000 hours oflight and water exposure according to ASTM D-1499-64.

Polyurethanes and poly(ureaurethane)s of the present invention can beformed into articles having a variety of shapes and dimensions, such asflat sheets or curved shapes. Non-limiting examples of useful methodsfor forming articles include heat treatment, pressure casting, orpouring liquid polyurethane or poly(ureaurethane) into a mold and curingthe product to form a molded article.

Generally, the polyurethanes and poly(ureaurethane)s of the presentinvention comprise a reaction product of components comprising at leastone polyisocyanate and at least one aliphatic polyol having 4 to 18carbon atoms and at least 2 or at least 3 hydroxyl groups, wherein atleast one of the polyisocyanate(s) and/or the aliphatic polyol(s) isbranched.

In the present invention, at least one of the isocyanate and/or at leastone of the polyols is branched. As used herein, “branched” means a chainof atoms with one or more side chains attached to it. Branching occursby the replacement of a substituent, e.g, a hydrogen atom, with acovalently bonded substituent or moiety, e.g, an alkyl group. While notintending to be bound by any theory, it is believed that branching ofthe polyisocyanate and/or polyol can increase the free volume within thepolymer matrix, thereby providing room for the molecules to move. Themolecules can orient and rotate into configurations and alignmentshaving favorable energy states which can provide good impact propertiesand/or high modulus of elasticity for the cured polymer matrix. As shownin FIGS. 1, 2 and 3, Dynamic Mechanical Analysis (DMA) of polyurethanecastings prepared according to Examples 1, 2 and 40, respectively, forloss modulus as a function of temperature show a low temperaturetransition at about −70° C. DMA analysis was conducted over atemperature range of −65° F. (−18° C.) to 350° F. (177° C.) undernitrogen according to ASTM D 4065-01. While not intending to be bound byany theory, it is believed that this low temperature transition is dueto molecular torsional mobility at that temperature and is believed tocontribute to the high impact strength of these polymers.

When a viscoelastic material is subjected to an oscillatory vibration,some energy is stored in the polymer, which is proportional to theelastic component of the modulus G′, or storage modulus, and some of theenergy is converted to heat through internal friction, or viscousdissipation of the energy, which is termed the loss modulus G″. Themaximum in the loss modulus is termed tan delta, which is the maximum ininternal friction, damping, or viscous energy dissipation.

High light transmittance, glassy polymers rarely exhibit high impactstrength. Polycarbonate plastics such as LEXAN can exhibit a similar lowtemperature transition, but can have lower impact strength and lowerYoung's modulus.

The physical properties of the polyurethanes and poly(ureaurethane)s ofthe present invention are derived from their molecular structure and aredetermined by the selection of building blocks, e.g., the selection ofthe reactants, the ratio of the hard crystalline and soft amorphoussegments, and the supra-molecular structures caused by atomicinteractions between chains.

Hard segments, i.e., the crystalline or semi-crystalline region of theurethane polymer, result from the reaction of the isocyanate and a chainextender, such as an aliphatic polyol having 4 to 18 carbon atoms or lowmolecular weight polyol having a molecular weight of less than about 200discussed herein. Generally, the soft segment, i.e., the amorphous,rubbery region of the urethane polymer, results from the reaction of theisocyanate and a polymer backbone component, for example a polyesterpolyol (such as a polycarbonate polyol) or a polyether polyol or shortchain diols that have not formed crystalline regions.

The qualitative contribution of a particular organic polyol to eitherthe hard or soft segment when mixed and reacted with otherpolyurethane-forming components can be readily determined by measuringthe Fischer microhardness of the resulting cured polyurethane accordingto ISO 14577-1:2002.

In some non-limiting embodiments, the hard segment content of thepolyurethane ranges from about 10 to about 100 weight percent, or about50 to about 100 weight percent, or about 70 to about 100 weight percent.The hard segment content is the percentage by weight of the hard segmentlinkages present in the polymer and can be calculated by determining thetotal number of equivalents, and from this the total weight of allreactants, and dividing the total weight of the hard segment linkagesobtainable from these reactants by the total weight of the reactantsthemselves. The following example will further explain the calculation.In Example I, Formulation 1 which follows, a polyurethane articleaccording to the invention was prepared by reacting 0.7 equivalents of1,4-butanediol, 0.3 equivalents of trimethylolpropane and one equivalentof 4,4′-methylene-bis-(cyclohexyl isocyanate) (DESMODUR W). Theequivalent weight of the 1,4-butanediol is 45 g/eq., the equivalentweight of the trimethylolpropane is 44.7 g/eq. (corrected forimpurities) and the equivalent weight of the DESMODUR W is 131.2 g/eq.Therefore, the actual weight of ingredients used is 31.54 parts byweight of 1,4-butanediol, 13.2 parts by weight of trimethylolpropane and131.2 parts by weight of DESMODUR W or a total reactant weight of 175.parts by weight. One equivalent of 1,4-butanediol will yield oneequivalent of hard segment linkage, where the hard segment linkage is1,4-butanediol/DESMODUR W dimer. The equivalent weight of a1,4-butanediol/DESMODUR W dimer linkage is 176 g/eq. so that the totalweight of the hard segment linkages determined by multiplying theequivalent weight of the hard segment dimer by the number of equivalentsof 1,4-butanediol would be 123.2 g/eq. Thus, the total weight of the1,4-butanediol/DESMODUR W dimer linkage, 123.2, divided by the totalweight of the reactants, 175.7, multiplied by 100 to convert topercentages would give a percentage by weight of hard segment linkage of70 percent by weight.

Both Plexiglas and stretched acrylic absorb quite a bit of water fromthe atmosphere. In accelerated tests such as QUV-B or soaking in waterat room temperature, surprisingly, polyurethanes according to thepresent invention including short chain diols such as butanediol andpentanediol, absorbed essentially no water in water vapor transmissionrate studies and after soaking in water for about 24 hours. While notintending to be bound by any theory, it is believed that even thoughthese plastics are very polar, the hydrogen bonding in the hard segmentdomains is strong enough to block water vapor transmission and uptake ofwater. In comparison, stretched acrylic will absorb enough water tocause severe swelling of the plastic, to the point that it cracksin-plane, like layers of onion skin separating until it falls apart. Thelow water absorption can also mitigate any hydrolysis degradation of theurethane groups in the polymer.

Discussion of the various aspects and embodiments of polyurethanes andpoly(ureaurethanes) of the present invention have been grouped generallyin groups A-Q below. As stated above, these groupings are not intendedto limit the scope of the invention and aspects of one grouping may berelevant to the subject matter of other groupings. Also, limitations asto amounts of reactants in one grouping are not necessarily intended tolimit amounts of the same component in other groupings, althoughappropriate amounts may be the same for a different grouping unlessotherwise indicated.

Group A

In some non-limiting embodiments, the present invention providespolyurethanes comprising a reaction product of components comprising:

-   -   (a) about 1 equivalent of at least one polyisocyanate;    -   (b) about 0.05 to about 0.9 equivalents of at least one branched        polyol having 4 to 18 carbon atoms and at least 3 hydroxyl        groups; and    -   (c) about 0.1 to about 0.95 equivalents of at least one diol        having 2 to 18 carbon atoms,        wherein the reaction product components are essentially free of        polyester polyol and polyether polyol and wherein the reaction        components are maintained at a temperature of at least about        100° C. for at least about 10 minutes.

As used herein, the term “equivalent” means the mass in grams of asubstance which will react with one mole (6.022×10²³ electrons) ofanother substance. As used herein, “equivalent weight” is effectivelyequal to the amount of a substance in moles, divided by the valence ornumber of functional reactive groups of the substance.

As used herein, the term “isocyanate” includes compounds, monomers,oligomers and polymers comprising at least one or at least two —N═C═Ofunctional groups and/or at least one or at least two —N═C═S(isothiocyanate) groups. Monofunctional isocyanates can be used as chainterminators or to provide terminal groups during polymerization. As usedherein, “polyisocyanate” means an isocyanate comprising at least two—N═C═O functional groups and/or at least two —N═C═S (isothiocyanate)groups, such as diisocyanates or triisocyanates, as well as dimers andtrimers or biurets of the isocyanates discussed herein. Suitableisocyanates are capable of forming a covalent bond with a reactive groupsuch as hydroxyl, thiol or amine functional group. Isocyanates useful inthe present invention can be branched or unbranched. As discussed above,use of branched isocyanates may be desirable to increase the free volumewithin the polymer matrix to provide space for the molecules to move.

Isocyanates useful in the present invention include “modified”,“unmodified” and mixtures of “modified” and “unmodified” isocyanates.The isocyanates can have “free”, “blocked” or partially blockedisocyanate groups. The term “modified” means that the aforementionedisocyanates are changed in a known manner to introduce biuret, urea,carbodiimide, urethane or isocyanurate groups or blocking groups. Insome non-limiting embodiments, the “modified” isocyanate is obtained bycycloaddition processes to yield dimers and trimers of the isocyanate,i.e., polyisocyanates. Free isocyanate groups are extremely reactive. Inorder to control the reactivity of isocyanate group-containingcomponents, the NCO groups may be blocked with certain selected organiccompounds that render the isocyanate group inert to reactive hydrogencompounds at room temperature. When heated to elevated temperatures,e.g., ranging from about 90° C. to about 200° C., the blockedisocyanates release the blocking agent and react in the same way as theoriginal unblocked or free isocyanate.

Generally, compounds used to block isocyanates are organic compoundsthat have active hydrogen atoms, e.g., volatile alcohols,epsilon-caprolactam or ketoxime compounds. Non-limiting examples ofsuitable blocking compounds include phenol, cresol, nonylphenol,epsilon-caprolactam and methyl ethyl ketoxime.

As used herein, the NCO in the NCO:OH ratio represents the freeisocyanate of free isocyanate-containing materials, and of blocked orpartially blocked isocyanate-containing materials after the release ofthe blocking agent. In some cases, it is not possible to remove all ofthe blocking agent. In those situations, more of the blockedisocyanate-containing material would be used to attain the desired levelof free NCO.

The molecular weight of the isocyanate and isothiocyanate can varywidely. In alternate non-limiting embodiments, the number averagemolecular weight (Mn) of each can be at least about 100 grams/mole, orat least about 150 grams/mole, or less than about 15,000 grams/mole, orless than about 5,000 grams/mole. The number average molecular weightcan be determined using known methods, such as by gel permeationchromatography (GPC) using polystyrene standards.

Non-limiting examples of suitable isocyanates include aliphatic,cycloaliphatic, aromatic and heterocyclic isocyanates, dimers andtrimers thereof and mixtures thereof. Useful cycloaliphatic isocyanatesinclude those in which one or more of the isocyanato groups are attacheddirectly to the cycloaliphatic ring and cycloaliphatic isocyanates inwhich one or more of the isocyanato groups are not attached directly tothe cycloaliphatic ring. Useful aromatic isocyanates include those inwhich one or more of the isocyanato groups are attached directly to thearomatic ring, and aromatic isocyanates in which one or more of theisocyanato groups are not attached directly to the aromatic ring. Usefulheterocyclic isocyanates include those in which one or more of theisocyanato groups are attached directly to the heterocyclic ring andheterocyclic isocyanates in which one or more of the isocyanato groupsare not attached directly to the heterocyclic ring.

Cycloaliphatic diisocyanates are desirable for use in the presentinvention because they are not adversely affected by ultraviolet lightand can yield polyurethanes having high impact energy absorption levels,which make them desirable for glass replacements and bilayer safetyglass applications. Also, polyurethanes prepared with cycloaliphaticdiisocyanates are not adversely affected by conventional processingtemperatures. When an aromatic polyisocyanate is used, generally careshould be taken to select a material that does not cause thepolyurethane to color (e.g., yellow).

In some non-limiting embodiments, the aliphatic and cycloaliphaticdiisocyanates can comprise about 6 to about 100 carbon atoms linked in astraight chain or cyclized and having two isocyanate reactive endgroups.

Non-limiting examples of suitable aliphatic isocyanates include straightchain isocyanates such as ethylene diisocyanate, trimethylenediisocyanate, 1,6-hexamethylene diisocyanate (HDI), tetramethylenediisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate,nonamethylene diisocyanate, decamethylene diisocyanate,1,6,11-undecanetriisocyanate, 1,3,6-hexamethylene triisocyanate,bis(isocyanatoethyl)-carbonate, bis(isocyanatoethyl)ether.

Other non-limiting examples of suitable aliphatic isocyanates includebranched isocyanates such as trimethylhexane diisocyanate,trimethylhexamethylene diisocyanate (TMDI), 2,2′-dimethylpentanediisocyanate, 2,2,4-trimethylhexane diisocyanate,2,4,4,-trimethylhexamethylene diisocyanate,1,8-diisocyanato-4-(isocyanatomethyl)octane,2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane,2-isocyanatopropyl-2,6-diisocyanatohexanoate, lysinediisocyanate methylester and lysinetriisocyanate methyl ester.

Non-limiting examples of suitable cycloaliphatic isocyanates includedinuclear compounds bridged by an isopropylidene group or an alkylenegroup of 1 to 3 carbon atoms. Non-limiting examples of suitablecycloaliphatic isocyanates include1,1′-methylene-bis-(4-isocyanatocyclohexane) or4,4′-methylene-bis-(cyclohexyl isocyanate) (such as DESMODUR Wcommercially available from Bayer Corp. of Pittsburgh, Pa.),4,4′-isopropylidene-bis-(cyclohexyl isocyanate), 1,4-cyclohexyldiisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (a branched isocyanate alsoknown as isophorone diisocyanate or IPDI) which is commerciallyavailable from Arco Chemical Co. of Newtown Square, Pa. andmeta-tetramethylxylylene diisocyanate (a branched isocyanate also knownas 1,3-bis(1-isocyanato-1-methylethyl)-benzene which is commerciallyavailable from Cytec Industries Inc. of West Patterson, N.J. under thetradename TMXDI® (Meta) Aliphatic Isocyanate) and mixtures thereof.

Other useful dinuclear cycloaliphatic diisocyanates include those formedthrough an alkylene group of from 1 to 3 carbon atoms inclusive, andwhich can be substituted with nitro, chlorine, alkyl, alkoxy and othergroups that are not reactive with hydroxyl groups (or active hydrogens)providing they are not positioned so as to render the isocyanate groupunreactive. Also, hydrogenated aromatic diisocyanates such ashydrogenated toluene diisocyanate may be used. Dinuclear diisocyanatesin which one of the rings is saturated and the other unsaturated, whichare prepared by partially hydrogenating aromatic diisocyanates such asdiphenyl methane diisocyanates, diphenyl isopropylidene diisocyanate anddiphenylene diisocyanate, may also be used.

Mixtures of cycloaliphatic diisocyanates with aliphatic diisocyanatesand/or aromatic diisocyanates may also be used. An example is4,4′-methylene-bis-(cyclohexyl isocyanate) with commercial isomermixtures of toluene diisocyanate or meta-phenylene diisocyanate.

Thioisocyanates corresponding to the above diisocyanates can be used, aswell as mixed compounds containing both an isocyanate and athioisocyanate group.

Non-limiting examples of suitable isocyanates can include but are notlimited to DESMODUR W, DESMODUR N 3300 (hexamethylene diisocyanatetrimer), DESMODUR N 3400 (60% hexamethylene diisocyanate dimer and 40%hexamethylene diisocyanate trimer), which are commercially availablefrom Bayer Corp.

In some non-limiting embodiments, the isocyanate can include1,1′-methylene-bis-(4-isocyanatocyclohexane) (also known as4,4′-methylene-bis-(cyclohexyl isocyanate)) and isomeric mixturesthereof. As used herein, the term “isomeric mixtures” refers to amixture of the cis-cis, trans-trans, and cis-trans isomers of theisocyanate. Non-limiting examples of isomeric mixtures suitable for usein the present invention can include the trans-trans isomer of4,4′-methylenebis(cyclohexyl isocyanate), hereinafter referred to as“PICM” (paraisocyanato cyclohexylmethane), the cis-trans isomer of PICM,the cis-cis isomer of PICM, and mixtures thereof. Three suitable isomersof 4,4′-methylenebis(cyclohexyl isocyanate) (also known as1,1′-methylenebis(4-isocyanatocyclohexane) for use in the presentinvention are shown below.

In some non-limiting embodiments, the PICM used in this invention can beprepared by phosgenating the 4,4′-methylenebis(cyclohexyl amine) (PACM)by procedures well known in the art such as the procedures disclosed inU.S. Pat. Nos. 2,644,007 and 2,680,127 which are incorporated herein byreference. The PACM isomer mixtures, upon phosgenation, can produce PICMin a liquid phase, a partially liquid phase, or a solid phase at roomtemperature. The PACM isomer mixtures can be obtained by thehydrogenation of methylenedianiline and/or by fractional crystallizationof PACM isomer mixtures in the presence of water and alcohols such asmethanol and ethanol.

In some non-limiting embodiments, the isomeric mixture can comprise fromabout 10 to about 100 weight percent of the trans, trans isomer of4,4′-methylenebis(cyclohexyl isocyanate)(PICM), or about 30 to about 100weight percent, or about 50 to about 100 weight percent, or about 75 toabout 100 weight percent. In other non-limiting embodiments, thecycloaliphatic isocyanate can consist essentially of the trans, transisomer of 1,1′-methylene-bis-(4-isocyanatocyclohexane) (also known as4,4′-methylene-bis-(cyclohexyl isocyanate)), e.g., at least about 80weight percent of the trans, trans isomer of1,1′-methylene-bis-(4-isocyanatocyclohexane), or at least about 90weight percent of the trans, trans isomer of1,1′-methylene-bis-(4-isocyanatocyclohexane), or at least about 95weight percent of the trans, trans isomer of1,1′-methylene-bis-(4-isocyanatocyclohexane) and in other non-limitingembodiments consists of about 100 weight percent of the trans, transisomer of 1,1′-methylene-bis-(4-isocyanatocyclohexane).

Non-limiting examples of suitable polyisocyanates for use in the presentinvention include polyisocyanates and polyisothiocyanates havingbackbone linkages such as urethane linkages (—NH—C(O)—O—), thiourethanelinkages (—NH—C(O)—S—), thiocarbamate linkages (—NH—C(S)—O—),dithiourethane linkages (—NH—C(S)—S—), polyamide linkages, andcombinations thereof.

Other non-limiting examples of suitable polyisocyanates includeethylenically unsaturated polyisocyanates and polyisothiocyanates;alicyclic polyisocyanates and polyisothiocyanates; aromaticpolyisocyanates and polyisothiocyanates wherein the isocyanate groupsare not bonded directly to the aromatic ring, e.g., α,α′-xylylenediisocyanate; aromatic polyisocyanates and polyisothiocyanates whereinthe isocyanate groups are bonded directly to the aromatic ring, e.g.,benzene diisbcyanate; aliphatic polyisocyanates and polyisothiocyanatescontaining sulfide linkages; aromatic polyisocyanates andpolyisothiocyanates containing sulfide or disulfide linkages; aromaticpolyisocyanates and polyisothiocyanates containing sulfone linkages;sulfonic ester-type polyisocyanates and polyisothiocyanates, e.g.,4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanato-phenol ester;aromatic sulfonic amide-type polyisocyanates and polyisothiocyanates;sulfur-containing heterocyclic polyisocyanates and polyisothiocyanates,e.g., thiophene-2,5-diisocyanate; halogenated, alkylated, alkoxylated,nitrated, carbodiimide modified, urea modified and biuret modifiedderivatives of isocyanates; and dimerized and trimerized products ofisocyanates.

Non-limiting examples of suitable ethylenically unsaturatedpolyisocyanates include butene diisocyanate and1,3-butadiene-1,4-diisocyanate. Non-limiting examples of suitablealicyclic polyisocyanates include isophorone diisocyanate, cyclohexanediisocyanate, methylcyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane,bis(isocyanatocyclohexyl)-2,2-propane,bis(isocyanatocyclohexyl)-1,2-ethane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptaneand2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane.

Non-limiting examples of suitable aromatic polyisocyanates wherein theisocyanate groups are not bonded directly to the aromatic ring includeα,α′-xylene diisocyanate, bis(isocyanatoethyl)benzene,α,α,α′,α′-tetramethylxylene diisocyanate,1,3-bis(1-isocyanato-1-methylethyl)benzene, bis(isocyanatobutyl)benzene,bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether,bis(isocyanatoethyl)phthalate, mesitylene triisocyanate and2,5-di(isocyanatomethyl)furan.

Non-limiting examples of suitable aromatic polyisocyanates havingisocyanate groups bonded directly to the aromatic ring include phenylenediisocyanate, ethylphenylene diisocyanate, isopropylphenylenediisocyanate, dimethylphenylene diisocyanate, diethylphenylenediisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzene diisocyanate, benzene triisocyanate, naphthalenediisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate,ortho-toluidine diisocyanate, ortho-tolylidine diisocyanate,ortho-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate,bis(3-methyl-4-isocyanatophenyl)methane, bis(isocyanatophenyl)ethylene,3,3′-dimethoxy-biphenyl-4,4′-diisocyanate, triphenylmethanetriisocyanate, polymeric 4,4′-diphenylmethane diisocyanate, naphthalenetriisocyanate, diphenylmethane-2,4,4′-triisocyanate,4-methyldiphenylmethane-3,5,2′,4′,6′-pentaisocyanate, diphenyletherdiisocyanate, bis(isocyanatophenylether)ethyleneglycol,bis(isocyanatophenylether)-1,3-propyleneglycol, benzophenonediisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate anddichlorocarbazole diisocyanate.

In some non-limiting embodiments, sulfur-containing isocyanates of thefollowing general formula (I) can be used:

wherein R₁₀ and R₁₁ are each independently C₁ to C₃ alkyl.

Non-limiting examples of suitable aliphatic polyisocyanates containingsulfide linkages include thiodiethyl diisocyanate, thiodipropyldiisocyanate, dithiodihexyl diisocyanate, dimethylsulfone diisocyanate,dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyldiisocyanate and dicyclohexylsulfide-4,4′-diisocyanate. Non-limitingexamples of aromatic polyisocyanates containing sulfide or disulfidelinkages include but are not limited todiphenylsulfide-2,4′-diisocyanate, diphenylsulfide-4,4′-diisocyanate,3,3′-dimethoxy-4,4′-diisocyanatodibenzyl thioether,bis(4-isocyanatomethylbenzene)-sulfide,diphenyldisulfide-4,4′-diisocyanate,2,2′-dimethyidiphenyidisulfide-5,5′-diisocyanate,3,3′-dimethyidiphenyidisulfide-5,5′-diisocyanate,3,3′-dimethyldiphenyldisulfide-6,6′-diisocyanate,4,4′-dimethyldiphenyidisulfide-5,5′-diisocyanate,3,3′-dimethoxydiphenyldisulfide-4,4′-diisocyanate and4,4′-dimethoxydiphenyldisulfide-3,3′-diisocyanate.

Non-limiting examples of suitable aromatic polyisocyanates containingsulfone linkages include diphenylsulfone-4,4′-diisocyanate,diphenylsulfone-3,3′-diisocyanate, benzidinesulfone-4,4′-diisocyanate,diphenylmethanesulfone-4,4′-diisocyanate,4-methyldiphenylmethanesulfone-2,4′-diisocyanate,4,4′-dimethoxydiphenylsulfone-3,3′-diisocyanate,3,3′-dimethoxy-4,4′-diisocyanatodibenzylsulfone,4,4′-dimethyidiphenylsulfone-3,3′-diisocyanate,4,4′-di-tert-butyl-diphenylsulfone-3,3′-diisocyanate and4,4′-dichlorodiphenylsulfone-3,3′-diisocyanate.

Non-limiting examples of aromatic sulfonic amide-type polyisocyanatesinclude4-methyl-3-isocyanato-benzene-sulfonylanilide-3′-methy14′-isocyanate,dibenzenesulfonyl-ethylenediamine-4,4′-diisocyanate,4,4′-methoxybenzenesulfonyl-ethylenediamine-3,3′-diisocyanate and4-methyl-3-isocyanato-benzene-sulfonylanilide-4-ethyl-3′-isocyanate.

Non-limiting examples of suitable isothiocyanates include cyclohexanediisothiocyanates; aromatic isothiocyanates wherein the isothiocyanategroup(s) are not bonded directly to the aromatic ring; aromaticisothiocyanates wherein the isothiocyanate group(s) are bonded directlyto the aromatic ring; heterocyclic isothiocyanates; carbonylpolyisothiocyanates; aliphatic polyisothiocyanates containing sulfidelinkages; and mixtures thereof.

Other non-limiting examples of suitable isothiocyanates include aromaticpolyisothiocyanates wherein the isothiocyanate groups are bondeddirectly to the aromatic ring, such as phenylene diisothiocyanate;heterocyclic polyisothiocyanates, such as2,4,6-triisothicyanato-1,3,5-triazine andthiophene-2,5-diisothiocyanate; carbonyl polyisothiocyanates; aliphaticpolyisothiocyanates containing sulfide linkages, such asthiobis(3-isothiocyanatopropane); aromatic polyisothiocyanatescontaining sulfur atoms in addition to those of the isothiocyanategroups; halogenated, alkylated, alkoxylated, nitrated, carbodiimidemodified, urea modified and biuret modified derivatives of thesepolyisothiocyanates; and dimerized and trimerized products of theseisothiocyanates.

Non-limiting examples of suitable aliphatic polyisothiocyanates include1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane,1,4-diisothiocyanatobutane and 1,6-diisothiocyanatohexane. Non-limitingexamples of aromatic polyisothiocyanates having isothiocyanate groupsbonded directly to the aromatic ring include1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene,1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene,2,5-diisothiocyanato-m-xylene, 4,4′-diisothiocyanato-1,1′-biphenyl,1,1′-methylenebis(4-isothiocyanatobenzene),1,1′-methylenebis(4-isothiocyanato-2-methylbenzene),1,1′-methylenebis(4-isothiocyanato-3-methylbenzene),1,1′-(1,2-ethane-diyl)bis(4-isothiocyanatobenzene),4,4′-diisothiocyanatobenzophenenone,4,4′-diisothiocyanato-3,3′-dimethylbenzophenone,benzanilide-3,4′-diisothiocyanate, diphenylether4,4′-diisothiocyanateand diphenylamine4,4′-diisothiocyanate.

Non-limiting examples of suitable carbonyl isothiocyanates includehexane-dioyl diisothiocyanate, nonanedioyl diisothiocyanate, carbonicdiisothiocyanate, 1,3-benzenedicarbonyl diisothiocyanate,1,4-benzenedicarbonyl diisothiocyanate and(2,2′-bipyridine)-4,4′-dicarbonyl diisothiocyanate. Non-limitingexamples of suitable aromatic polyisothiocyanates containing sulfuratoms in addition to those of the isothiocyanate groups, include1-isothiocyanato-4-[(2-isothiocyanato)sulfonyl]benzene,thiobis(4-isothiocyanatobenzene), sulfonylbis(4-isothiocyanatobenzene),sulfinylbis(4-isothiocyanatobenzene),dithiobis(4-isothiocyanatobenzene),4-isothiocyanato-1-[(4-isothiocyanatophenyl)-sulfonyl]-2-methoxybenzene,4-methyl-3-isothicyanatobenzene-sulfonyl-4′-isothiocyanate phenyl esterand4-methyl-3-isothiocyanatobenzene-sulfonylanilide-3′-methyl-4′-isothiocyanate.

Other non-limiting examples of isocyanates having isocyanate andisothiocyanate groups include materials having aliphatic, alicyclic,aromatic or heterocyclic groups and which optionally can contain sulfuratoms in addition to those of the isothiocyanate groups. Non-limitingexamples of such materials include 1-isocyanato-3-isothiocyanatopropane,1-isocyanato-5-isothiocyanatopentane,1-isocyanato-6-isothiocyanatohexane, isocyanatocarbonyl isothiocyanate,1-isocyanato-4-isothiocyanatocyclohexane,1-isocyanato-4-isothiocyanatobenzene,4-methyl-3-isocyanato-1-isothiocyanatobenzene,2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine,4-isocyanato-4′-isothiocyanato-diphenyl sulfide and2-isocyanato-2′-isothiocyanatodiethyl disulfide.

In some non-limiting embodiments, the isocyanate comprises at least onetriisocyanate or at least one polyisocyanate trimer. Non-limitingexamples of such isocyanates include aromatic triisocyanates such astris(4-iso-cyanatophenyl)methane (DESMODUR R),1,3,5-tris(3-isocyanato-4-methylphenyl)-2,3,6-trioxohexahydro-1,3,5triazine (DESMODUR IL); adducts of aromatic diisocyanates such as theadduct of 2,4-tolylene diisocyanate (TDI, 2,4-diisocyanatotoluene) andtrimethylolpropane (DESMODUR L); and from aliphatic triisocyanates suchas N-isocyanatohexylaminocarbonyl-N,N′-bis(isocyanatohexyl)urea(DESMODUR N),2,4,6-trioxo-1,3,5-tris(6-isocyanatohexyl)hexahydro-1,3,5-triazine(DESMODUR N3390),2,4,6-trioxo-1,3,5-tris(5-isocyanato-1,3,3-trimethylcyclo-hexylmethyl)hexahydro-1,3,5-triazine(DESMODUR Z4370), and 4-(isocyanatomethyl)-1,8-octane diisocyanate. Theabove DESMODUR products are commercially available from Bayer Corp. Alsouseful are the biuret of hexanediisocyanate, polymeric methanediisocyanate, and polymeric isophorone diisocyanate. Trimers ofhexamethylene diisocyanate, isophorone diisocyanate andtetramethylxylylene diisocyanate

In some non-limiting embodiments, the polyisocyanate used to make apolyurethane polyol prepolymer as a precursor is a cycloaliphaticcompound, such as a dinuclear compound bridged by an isopropylidenegroup or an alkylene group of 1 to 3 carbon atoms.

The reaction components for preparing the polyurethane of Group A alsocomprise about 0.1 to about 0.9 equivalents of at least one branchedpolyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups. Asdiscussed above, the branched polyol may increase the free volume withinthe polymer matrix to provide space for the molecules to move or rotatewhen impacted.

As used herein, the term “polyol” includes compounds, monomers,oligomers and polymers comprising at least two hydroxyl groups (such asdiols) or at least three hydroxyl groups (such as triols), higherfunctional polyols and mixtures thereof. Suitable polyols are capable offorming a covalent bond with a reactive group such as an isocyanatefunctional group.

Non-limiting examples of suitable polyols include aliphatic,cycloaliphatic, aromatic, heterocyclic, oligomeric, and polymericpolyols and mixtures thereof. In some embodiments, such as fortransparencies or windows exposed to sunlight, aliphatic orcycloaliphatic polyols can be used.

The number of carbon atoms in the polyol described above for Group A canrange from 4 to 18, or from 4 to 12, or from 4 to 10, or from 4 to 8, orfrom 4 to 6 carbon atoms. In some non-limiting embodiments, one or morecarbon atoms in the polyol can be replaced with one or more heteroatoms,such as N, S, or O.

As discussed above, the branched polyol useful as a reaction product forpreparing the polyurethane of Group A has 4 to 18 carbon atoms and atleast 3 hydroxyl groups. Non-limiting examples of trifunctional,tetrafunctional or higher polyols suitable for use as the branchedpolyol include branched chain alkane polyols such as glycerol orglycerin, tetramethylolmethane, trimethylolethane (for example1,1,1-trimethylolethane), trimethylolpropane (TMP) (for example1,1,1-trimethylolpropane), erythritol,. pentaerythritol,dipentaerythritol, tripentaerythritol, sorbitan, alkoxylated derivativesthereof (discussed below) and mixtures thereof.

In some non-limiting embodiments, the polyol can be a cycloalkanepolyol, such as trimethylene bis(1,3,5-cyclohexanetriol).

In some non-limiting embodiments, the polyol can be an aromatic polyol,such as trimethylene bis(1,3,5-benzenetriol).

Further non-limiting examples of suitable polyols include theaforementioned polyols which can be alkoxylated derivatives, such asethoxylated, propoxylated and butoxylated. In alternate non-limitingembodiments, the following polyols can be alkoxylated with from 1 to 10alkoxy groups: glycerol, trimethylolethane, trimethylolpropane,benzenetriol, cyclohexanetriol, erythritol, pentaerythritol, sorbitol,mannitol, sorbitan, dipentaerythritol and tripentaerythritol. Inalternate non-limiting embodiments, alkoxylated, ethoxylated andpropoxylated polyols and mixtures thereof can be used alone or incombination with unalkoxylated, unethoxylated and unpropoxylated polyolshaving at least three hydroxyl groups and mixtures thereof. The numberof alkoxy groups can be from 1 to 10, or from 2 to 8 or any rationalnumber between 1 and 10. In a non-limiting embodiment, the alkoxy groupcan be ethoxy and the number of ethoxy groups can be 1 to 5 units. Inanother non-limiting embodiment, the polyol can be trimethylolpropanehaving up to 2 ethoxy groups. Non-limiting examples of suitablealkoxylated polyols include ethoxylated trimethylolpropane, propoxylatedtrimethylolpropane, ethoxylated trimethylolethane, and mixtures thereof.

Mixtures of any of the above polyols can be used.

In some embodiments, the polyurethanes of the present invention can bethermoplastics, for example those polyurethanes having a molecularweight per crosslink of at least about 6000 g/mole.

In some non-limiting embodiments, the branched polyol having 4 to 18carbon atoms can have a number average molecular weight of about 100 toabout 500 grams/mole. In some non-limiting embodiments, the polyol canhave a number average molecular weight of less than about 450grams/mole. In other non-limiting embodiments, the polyol can have anumber average molecular weight of less than about 200 grams/mole.

The reaction components for preparing the polyurethane of Group A alsocomprise about 0.1 to about 0.9 equivalents of at least one diol having2 to 18 carbon atoms, or from about 2 to about 14 carbon atoms, or from2 to 10 carbon atoms, or from 2 to 6 carbon atoms. In some non-limitingembodiments, one or more carbon atoms in the diol can be replaced withone or more heteroatoms, such as N, S, or O.

Non-limiting examples of suitable diols include straight chain alkanediols such as ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, 1,2-ethanediol, propane diols such as1,2-propanediol and 1,3-propanediol, butane diols such as1,2-butanediol, 1,3-butanediol, and 1,4-butanediol, pentane diols suchas 1,5-pentanediol, 1,3-pentanediol and 2,4-pentanediol, hexane diolssuch as 1,6-hexanediol and 2,5-hexanediol, heptane diols such as2,4-heptanediol, octane diols such as 1,8-octanediol, nonane diols suchas 1,9-nonanediol, decane diols such as 1,10-decanediol, dodecane diolssuch as 1,12-dodecanediol, octadecanediols such as 1,18-octadecanediol,sorbitol, mannitol, and mixtures thereof. In some non-limitingembodiments, the diol is a propane diol such as 1,2-propanediol and1,3-propanediol, or butane diol such as 1,2-butanediol, 1,3-butanediol,and 1,4-butanediol. In some non-limiting embodiments, one or more carbonatoms in the polyol can be replaced with one or more heteroatoms, suchas N, S, or O, for example sulfonated polyols, such as dithio-octane bisdiol, thiodiethanol such as 2,2-thiodiethanol, or3,6-dithia-1,2-octanediol.

Other non-limiting examples of suitable diols include those representedby the following formula:

wherein R represents C₀ to C₁₈ divalent linear or branched aliphatic,cycloaliphatic, aromatic, heterocyclic, or oligomeric saturated alkyleneradical or mixtures thereof; C₂ to C₁₈ divalent organic radicalcontaining at least one element selected from the group consisting ofsulfur, oxygen and silicon in addition to carbon and hydrogen atoms; C₅to C₁₈ divalent saturated cycloalkylene radical; or C₅ to C₁₈ divalentsaturated heterocycloalkylene radical; and R′ and R′ can be present orabsent and, if present, each independently represent C₁ to C₁₈ divalentlinear or branched aliphatic, cycloaliphatic, aromatic, heterocyclic,polymeric, or oligomeric saturated alkylene radical or mixtures thereof.

Other non-limiting examples of suitable diols include branched chainalkane diols, such as propylene glycol, dipropylene glycol, tripropyleneglycol, neopentyl glycol, 2-methyl-butanediol.2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol,2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, dibutyl 1,3-propanediol, polyalkyleneglycols such as polyethylene glycols, and mixtures thereof.

In some non-limiting embodiments, the diol can be a cycloalkane diol,such as cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanols(CHDM), such as 1,4-cyclohexanedimethanol, cyclododecanediol,4,4′-isopropylidene-biscyclohexanol, hydroxypropylcyclohexanol,cyclohexanediethanol, 1,2-bis(hydroxymethyl)-cyclohexane,1,2-bis(hydroxyethyl)-cyclohexane, 4,4′-isopropylidene-biscyclohexanol,bis(4-hydroxycyclohexanol)methane and mixtures thereof.

In some non-limiting embodiments, the diol can be an aromatic diol, suchas dihydroxybenzene, 1,4-benzenedimethanol, xylene glycol, hydroxybenzylalcohol and dihydroxytoluene; bisphenols, such as,4,4′-isopropylidenediphenol, 4,4′-oxybisphenol,4,4′-dihydroxybenzophenone, 4,4′-thiobisphenol, phenolphthalein,bis(4-hydroxyphenyl)methane, 4,4′-(1,2-ethenediyl)bisphenol and4,4′-sulfonylbisphenol; halogenated bisphenols, such as4,4′-isopropylidenebis(2,6-dibromophenol),4,4′-isopropylidenebis(2,6-dichlorophenol) and4,4′-isopropylidenebis(2,3,5,6-tetrachlorophenol); alkoxylatedbisphenols, which can have, for example, ethoxy, propoxy, α-butoxy andβ-butoxy groups; and biscyclohexanols, which can be prepared byhydrogenating the corresponding bisphenols, such as4,4′-isopropylidene-biscyclohexanol, 4,4′-oxybiscyclohexanol,4,4′-thiobiscyclohexanol and bis(4-hydroxycyclohexanol)methane, thealkoxylation product of 1 mole of 2,2-bis(4-hydroxyphenyl)propane (i.e.,bisphenol-A) and 2 moles of propylene oxide, hydroxyalkyl terephthalatessuch as meta or para bis(2-hydroxyethyl)terephthalate,bis(hydroxyethyl)hydroquinone and mixtures thereof.

In some non-limiting embodiments, the diol can be an heterocyclic diol,for example a dihydroxy piperidine such as1,4-bis(hydroxyethyl)piperazine.

In some non-limiting embodiments, the diol can be a diol of an amide oralkane amide (such as ethanediamide (oxamide)), for exampleN,N′,bis(2-hydroxyethyl)oxamide.

In some non-limiting embodiments, the diol can be a diol of apropionate, such as2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate.

In some non-limiting embodiments, the diol can be a diol of a hydantoin,such as bishydroxypropyl hydantoin.

In some non-limiting embodiments, the diol can be a diol of a phthalate,such as meta or para bis(2-hydroxyethyl)terephthalate.

In some non-limiting embodiments, the diol can be a diol of ahydroquinone, such as a dihydroxyethylhydroquinone.

In some non-limiting embodiments, the diol can be a diol of anisocyanurate, such as dihydroxyethyl isocyanurate.

In some non-limiting embodiments, the diol for use in the presentinvention can be an SH-containing material, such as polythiols having atleast three thiol groups and 4 to 18 carbon atoms. Non-limiting examplesof suitable polythiols can include but are not limited to aliphaticpolythiols, cycloaliphatic polythiols, aromatic polythiols, heterocyclicpolythiols, polymeric polythiols, oligomeric polythiols and mixturesthereof. The sulfur-containing active hydrogen-containing material canhave linkages including but not limited to ether linkages (—O—), sulfidelinkages (—S—), polysulfide linkages (—S_(x)—, wherein x is at least 2,or from 2 to 4) and combinations of such linkages. As used herein, theterms “thiol,” “thiol group,” “mercapto” or “mercapto group” refer to an—SH group which is capable of forming a thiourethane linkage, (i.e.,—NH—C(O)—S—) with an isocyanate group or a dithioruethane linkage (i.e.,—NH—C(S)—S—) with an isothiocyanate group.

In some non-limiting embodiments, the components of the polyurethane areessentially free of SH-containing materials, i.e., comprise less thanabout 5 weight percent of SH-containing materials, in other non-limitingembodiments comprise less than about 2 weight percent of SH-containingmaterials, and in other non-limiting embodiments are free ofSH-containing materials.

In some non-limiting embodiments, the diol having 4 to 18 carbon atomscan have a number average molecular weight of about 200 to about 10,000grams/mole, or less than about 500 grams/mole, or less than about 200grams/mole.

Mixtures of any of the above diols can be used.

In some non-limiting embodiments, the reaction components for preparingthe polyurethane of Group A can further comprise one or morenon-branched triols and/or one or more non-branched higher functionalpolyols.

Non-limiting examples of suitable non-branched triols and non-branchedhigher functional polyols include aliphatic, cycloaliphatic, aromatic,heterocyclic, oligomeric, and polymeric polyols and mixtures thereof.

In some non-limiting embodiments, the polyol can be a cycloalkanepolyol, such as cyclohexanetriol (for example 1,3,5-cyclohexanetriol).

In some non-limiting embodiments, the polyol can be an aromatic polyol,such as benzenetriol (for example 1,2,3-benzenetriol,1,2,4-benzenetriol, and 1,3,5-benzenetriol) and phenolphthalein.

In some non-limiting embodiments, the polyol can be a polyol of anisocyanurate, such as tris hydroxyethyl isocyanurate.

In some non-limiting embodiments, the reaction components for preparingthe polyurethane of Group A can further comprise one or more branched orunbranched polyols (diols, triols, and/or higher functional polyols)having more than 18 carbon atoms.

Non-limiting examples of suitable polyols having more than 18 carbonatoms include straight or branched chain aliphatic polyols,cycloaliphatic polyols, cycloaliphatic polyols, aromatic polyols,heterocyclic polyols, oligomeric polyols, polymeric polyols and mixturesthereof.

Non-limiting examples of suitable straight or branched chain aliphaticpolyols having more than 18 carbon atoms include 1,18-icosanediol and1,24-tetracosanediol.

Other non-limiting examples of suitable polyols having more than 18carbon atoms include those represented by the following formula:

wherein R represents C₀ to C₃₀ divalent linear or branched aliphatic,cycloaliphatic, aromatic, heterocyclic, or oligomeric saturated alkyleneradical or mixtures thereof; C₂ to C₃₀ divalent organic radicalcontaining at least one element selected from the group consisting ofsulfur, oxygen and silicon in addition to carbon and hydrogen atoms; C₅to C₃₀ divalent saturated cycloalkylene radical; or C₅ to C₃₀ divalentsaturated heterocycloalkylene radical; and R′ and R″ can be present orabsent and, if present, each independently represent C₁ to C₃₀ divalentlinear or branched aliphatic, cycloaliphatic, aromatic, heterocyclic,polymeric, or oligomeric saturated alkylene radical or mixtures thereof.

Non-limiting examples of suitable cycloaliphatic polyols having morethan 18 carbon atoms include biscyclohexanols having more than 18 carbonatoms, which can be prepared by hydrogenating the correspondingbisphenols.

Non-limiting examples of suitable aromatic polyols having more than 18carbon atoms include bisphenols, alkoxylated bisphenols, such asalkoxylated 4,4′-isopropylidenediphenol which can have from 3 to 70alkoxy groups, and

Other non-limiting examples of suitable oligomeric or polymeric polyolshaving more than 18 carbon atoms include higher polyalkylene glycolssuch as polyethylene glycols having number average molecular weightsranging from about 200 grams/mole to about 2,000 grams/mole, andmixtures thereof.

In some non-limiting embodiments, the polyol for use in the presentinvention can be an SH-containing material, such as polythiols having atleast two thiol groups or at least three thiol groups and at least 18carbon atoms. Non-limiting examples of suitable polythiols can includebut are not limited to aliphatic polythiols, cycloaliphatic polythiols,aromatic polythiols, heterocyclic polythiols, polymeric polythiols,oligomeric polythiols and mixtures thereof. The sulfur-containing activehydrogen-containing material can have linkages including but not limitedto ether linkages (—O—), sulfide linkages (—S—), polysulfide linkages(—S_(x)—, wherein x is at least 2, or from 2 to 4) and combinations ofsuch linkages. As used herein, the terms “thiol,” “thiol group,”“mercapto” or “mercapto group” refer to an —SH group which is capable offorming a thiourethane linkage, (i.e., —NH—C(O)—S—) with an isocyanategroup or a dithioruethane linkage (i.e., —NH—C(S)—S—) with anisothiocyanate group.

In some non-limiting embodiments, the components of the polyurethane areessentially free of SH-containing materials, e.g., contain less thanabout 5 weight percent of SH-containing materials, in other non-limitingembodiments contain less than about 2 weight percent of SH-containingmaterials, and in other non-limiting embodiments are free ofSH-containing materials.

In some non-limiting embodiments, the polyol having at least 18 carbonatoms can have a number average molecular weight of about 200 to about5,000 grams/mole, or about 200 to about 4,000 grams/mole, or at leastabout 200 grams/mole, or at least about 400 grams/mole, or at leastabout 1000 grams/mole, or at least about 2000 grams/mole. In somenon-limiting embodiments, the polyol can have a number average molecularweight of less than about 5,000 grams/mole, or less than about 4,000grams/mole, or less than about 3,000 grams/mole, or less than about2,000 grams/mole, or less than about 1,000 grams/mole, or less thanabout 500 grams/mole.

Mixtures of any of the above polyols can be used. For example, thepolyol can comprise trimethylolpropane and the diol can comprisebutanediol and/or pentanediol.

As discussed above, the amount of branched polyol used to form thepolyurethane of Group A is about 0.1 to about 0.9 equivalents. In somenon-limiting embodiments, the amount of branched polyol used to form thepolyurethane is about 0.3 to about 0.9 equivalents. In othernon-limiting embodiments, the amount of branched polyol used to form thepolyurethane is about 0.3 equivalents.

As discussed above, the amount of diol used to form the polyurethane ofGroup A is about 0.1 to about 0.9 equivalents. In some non-limitingembodiments, the amount of diol used to form the polyurethane is about0.3 to about 0.9 equivalents. In other non-limiting embodiments, theamount of diol used to form the polyurethane is about 0.3 equivalents.

In some non-limiting embodiments of the polyurethane of Group A, thereaction components comprise about 0.1 to about 0.9 equivalents of atleast one branched polyol having 4 to 18 carbon atoms and at least 3hydroxyl groups and about 0.1 to about 0.9 equivalents of at least onediol having 2 to 18 carbon atoms, per 1 equivalent of at least onepolyisocyanate, wherein the reaction product components are essentiallyfree of polyester polyol and polyether polyol and wherein the reactioncomponents are maintained at a temperature of at least about 100° C. forat least about 10 minutes.

In some non-limiting embodiments, the polyurethane comprises a reactionproduct of components consisting of: about 1 equivalent of4,4′-methylene-bis-(cyclohexyl isocyanate); about 0.3 to about 0.5equivalents of trimethylolpropane; and about 0.3 to about 0.7equivalents of butanediol or pentanediol, or about 0.7 equivalents ofbutanediol or pentanediol, wherein the reaction components aremaintained at a temperature of at least about 100° C. for at least about10 minutes.

In another embodiment, the present invention provides polyurethanes ofGroup A comprising a reaction product of components consisting of: about1 equivalent of 4,4′-methylene-bis-(cyclohexyl isocyanate); about 0.3equivalents of trimethylolpropane; and about 0.7 equivalents of1,10-dodecanediol, wherein the reaction components are maintained at atemperature of at least about 100° C. for at least about 10 minutes.

In another embodiment, the present invention provides polyurethanes ofGroup A comprising a reaction product of components consisting of: about1 equivalent of 4,4′-methylene-bis-(cyclohexyl isocyanate); about 0.3equivalents of trimethylolpropane; and about 0.7 equivalents of1,5-pentanediol, wherein the reaction components are maintained at atemperature of at least about 100° C. for at least about 10 minutes.

In another embodiment, the present invention provides polyurethanes ofGroup A comprising a reaction product of components consisting of: about1 equivalent of 4,4′-methylene-bis-(cyclohexyl isocyanate); about 0.3equivalents of trimethylolpropane; about 0.7 equivalents of1,4-butanediol, wherein the reaction components are maintained at atemperature of at least about 100° C. for at least about 10 minutes.

In another embodiment, the present invention provides polyurethanes ofGroup A comprising a reaction product of components consisting of: about1 equivalent of 4,4′-methylene-bis-(cyclohexyl isocyanate); about 0.4equivalents of trimethylolpropane; about 0.6 equivalents of1,18-octadecanediol, wherein the reaction components are maintained at atemperature of at least about 100° C. for at least about 10 minutes.

The polyurethanes of Group A can exhibit good ballistics resistance,e.g., resistance to perforation, penetration or cracking due to impactfrom a projectile such as bullet or shot which is shot from a handgun,shotgun, rifle, AK-47, or other shooting device or explosives. In someembodiments, the polyurethanes of Group A of 0.75″ (1.9 cm) thickness orgreater will stop or deflect: a 9 mm, 125 grain bullet shot at aninitial velocity of 1350 ft/sec (411.5 m/sec) from 20 feet; a 0.40caliber bullet shot at an initial velocity of 987 ft/sec (300.8 m/sec)bullet from 20 feet (6.1 m); and/or a 12 gauge shotgun shot at aninitial velocity of 1290 ft/sec (393.2 m/sec) from 20 feet (6.1 m).

Group B

In some non-limiting embodiments, the present invention providespolyurethanes of Group B comprising a reaction product of componentscomprising: (a) an isocyanate functional urethane prepolymer comprisinga reaction product of components comprising: (i) about 1 equivalent ofat least one polyisocyanate; and (ii) about 0.1 to about 0.5 equivalentsof at least one diol having 2 to 18 carbon atoms; and (b) about 0.05 toabout 0.9 equivalents of at least one polyol having 4 to 18 carbon atomsand at least 3 hydroxyl groups; and (c) up to about 0.45 equivalents ofat least one diol having 2 to 18 carbon atoms, wherein the reactionproduct components are essentially free of polyester polyol andpolyether polyol.

Non-limiting examples and amounts of suitable polyisocyanates, diols andpolyols for use as reaction products for preparing the polyurethanes ofGroup B are discussed in detail above with respect to Group A. Methodsfor preparing polyurethanes of Group B are discussed in detail below.

Group C

In some non-limiting embodiments, the present invention providespolyurethanes of Group C comprising a reaction product of componentscomprising: at least one polyisocyanate selected from the groupconsisting of polyisocyanate trimers and branched polyisocyanates, thepolyisocyanate having at least three isocyanate functional groups; andat least one aliphatic polyol having 4 to 18 carbon atoms and at leasttwo hydroxyl groups, wherein the reaction product components areessentially free of polyester polyol and polyether polyol.

In other non-limiting embodiments, the present invention providespolyurethanes of Group C comprising a reaction product of componentsconsisting of: about 1 equivalent of 4,4′-methylene-bis-(cyclohexylisocyanate); about 1.1 equivalents of butanediol; and about 0.1equivalents of isophorone diisocyanate trimer.

Non-limiting examples of suitable polyisocyanate trimers, branchedpolyisocyanates and aliphatic polyols (including but not limited tostraight chain, branched or cycloaliphatic polyols) for use in asreaction products for preparing the polyurethanes of Group C arediscussed in detail above with respect to Group A. Similar amounts ofpolyisocyanate trimer(s) and/or branched polyisocyanate(s) can be usedas described for the polyisocyanate of Group A above. Also, mixtures ofpolyisocyanate trimer(s) and/or branched polyisocyanate(s) with othernon-branched and non-trimer polyisocyanates described above can be usedto form the polyurethanes of Group C.

In some non-limiting embodiments of the polyurethane of Group C, thereaction components comprise about 0.1 to about 0.9 equivalents of atleast one branched polyol having 4 to 18 carbon atoms and at least 2hydroxyl groups per 1 equivalent of at least one polyisocyanate, and inother non-limiting embodiments about 0.3 to about 0.9 equivalents of atleast one aliphatic polyol having 2 to 18 carbon atoms, wherein thereaction product components are essentially free of polyester polyol andpolyether polyol.

As discussed above, in some non-limiting embodiments of Group A, Group Band Group C, the reaction product components are essentially free ofpolyester polyol and polyether polyol. As used herein, “essentially freeof polyester polyol and polyether polyol” means that the reactionproduct components comprise less than about 10 weight percent ofpolyester polyol and/or polyether polyol, or less than about 5 weightpercent of polyester polyol and/or polyether polyol, or less than about2 weight percent of polyester polyol and/or polyether polyol or is freeof polyester polyol and/or polyether polyol.

Non-limiting examples of such polyester polyols include polyesterglycols, polycaprolactone polyols, polycarbonate polyols and mixturesthereof. Polyester glycols can include the esterification products ofone or more dicarboxylic acids having from four to ten carbon atoms,such as but not limited to adipic, succinic or sebacic acids, with oneor more low molecular weight glycols having from two to ten carbonatoms, such as but not limited to ethylene glycol, propylene glycol,diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and1,10-decanediol. Esterification procedures for producing polyesterpolyols are described, for example, in the article D. M. Young, F.Hostettler et al., “Polyesters from Lactone,” Union Carbide F-40, p.147.

Non-limiting examples of polycaprolactone polyols include those preparedby condensing caprolactone in the presence of difunctional activehydrogen material such as water or low molecular weight glycols, forexample ethylene glycol and propylene glycol. Non-limiting examples ofsuitable polycaprolactone polyols can include commercially availablematerials designated as the CAPA series from Solvay Chemical of Houston,Tex. such as CAPA 2047A and CAPA 2077A, and the TONE series from DowChemical of Midland, Mich. such as TONE 0201, 0210, 0230 & 0241. In somenon-limiting embodiments, the polycaprolactone polyol has a molecularweight ranging from about 500 to about 2000 grams per mole, or about 500to about 1000 grams per mole.

Non-limiting examples of polycarbonate polyols include aliphaticpolycarbonate diols, for example those based upon alkylene glycols,ether glycols, alicyclic glycols or mixtures thereof. In someembodiments, the alkylene groups for preparing the polycarbonate polyolcan comprise from 5 to 10 carbon atoms and can be straight chain,cycloalkylene or combinations thereof. Non-limiting examples of suchalkylene groups include hexylene, octylene, decylene, cyclohexylene andcyclohexyldimethylene. Suitable polycarbonate polyols can be prepared,in non-limiting examples, by reacting a hydroxy terminated alkyleneglycol with a dialkyl carbonate, such as methyl, ethyl, n-propyl orn-butyl carbonate, or diaryl carbonate, such as diphenyl or dinaphthylcarbonate, or by reacting of a hydroxy-terminated alkylene diol withphosgene or bischoloroformate, in a manner well known to those skilledin the art. Non-limiting examples of such polycarbonate polyols includethose commercially available as Ravecarb™ 107 from Enichem S.p.A.(Polimeri Europa) of Italy and polyhexylene carbonate diols, about 1000number average molecular weight, such as KM10-1733 polycarbonate diolprepared from hexanediol, available from Stahl. Examples of othersuitable polycarbonate polyols that are commercially available includeKM10-1122, KM10-1667 (prepared from a 50/50 weight percent mixture ofcyclohexane dimethanol and hexanediol) (commercially available fromStahl U.S.A. Inc. of Peabody, Mass.) and DESMOPHEN 2020E (commerciallyavailable from Bayer Corp).

The polycarbonate polyol can be produced by reacting diol, such asdescribed herein, and a dialkyl carbonate, such as described in U.S.Pat. No. 4,160,853. The polycarbonate polyol can includepolyhexamethylene carbonate such as HO—(CH₂)₆-[O—C(O)—O—(CH₂)₆]n—OH,wherein n is an integer from 4 to 24, or from 4 to 10, or from 5 to 7.

Non-limiting examples of polyether polyols include poly(oxyalkylene)polyols or polyalkoxylated polyols. Poly(oxyalkylene)polyols can beprepared in accordance with known methods. In a non-limiting embodiment,a poly(oxyalkylene)polyol can be prepared by condensing an alkyleneoxide, or a mixture of alkylene oxides, using acid- or base-catalyzedaddition with a polyhydric initiator or a mixture of polyhydricinitiators, such as ethylene glycol, propylene glycol, glycerol, andsorbitol. Compatible mixtures of polyether polyols can also be used. Asused herein, “compatible” means that two or more materials are mutuallysoluble in each other so as to essentially form a single phase.Non-limiting examples of alkylene oxides can include ethylene oxide,propylene oxide, butylene oxide, amylene oxide, aralkylene oxides, suchas styrene oxide, mixtures of ethylene oxide and propylene oxide. Insome non-limiting embodiments, polyoxyalkylene polyols can be preparedwith mixtures of alkylene oxide using random or step-wise oxyalkylation.Non-limiting examples of such poly(oxyalkylene)polyols includepolyoxyethylene polyols, such as polyethylene glycol, andpolyoxypropylene polyols, such as polypropylene glycol.

Other polyether polyols include block polymers such as those havingblocks of ethylene oxide-propylene oxide and/or ethylene oxide-butyleneoxide. In some non-limiting embodiments, the polyether polyol comprisesa block copolymer of the following formula:HO—(CHR₁CHR₂—O)_(a)—(CHR₃CHR₄—O)_(b)—(CHR₅CHR₆—O)_(c)—Hwherein R₁ through R₆ can each independently represent hydrogen ormethyl; and a, b, and c can each be independently selected from aninteger from 0 to 300, wherein a, b and c are selected such that thenumber average molecular weight of the polyol is less than about 32,000grams/mole, or less than about 10,000 grams/mole, as determined by GPC.In other non-limiting embodiments a, b, and c each can be independentlyan integer from 1 to 300. In other non-limiting embodiments, R₁, R₂, R₅,and R₆ can be hydrogen, and R₃ and R₄ each can be independently selectedfrom hydrogen and methyl, with the proviso that R₃ and R₄ are differentfrom one another. In other non-limiting embodiments, R₃ and R₄ can behydrogen, and R₁ and R₂ each can be independently selected from hydrogenand methyl, with the proviso that R₁ and R₂ are different from oneanother, and R₅ and R₆ each can be independently selected from hydrogenand methyl, with the proviso that R₅ and R₆ are different from oneanother.

In some non-limiting embodiments, polyalkoxylated polyols can berepresented by the following general formula:

wherein m and n can each be a positive integer, the sum of m and n beingfrom 5 to 70; R₁ and R₂ are each hydrogen, methyl or ethyl; and A is adivalent linking group such as a straight or branched chain alkylenewhich can contain from 1 to 8 carbon atoms, phenylene, and C₁ to C₉alkyl-substituted phenylene. The values of m and n can, in combinationwith the selected divalent linking group, determine the molecular weightof the polyol. Polyalkoxylated polyols can be prepared by methods thatare known in the art. In a non-limiting embodiment, a polyol such as4,4′-isopropylidenediphenol can be reacted with an oxirane-containingmaterial such as ethylene oxide, propylene oxide or butylene oxide, toform what is commonly referred to as an ethoxylated, propoxylated orbutoxylated polyol having hydroxyl functionality. Non-limiting examplesof polyols suitable for use in preparing polyalkoxylated polyols caninclude those polyols described in U.S. Pat. No. 6,187,444 B1 at column10, lines 1-20, incorporated herein by reference.

In some non-limiting embodiments, the polyether polyol can be PLURONICethylene oxide/propylene oxide block copolymers, such as PLURONIC R andPLURONIC L62D, and/or TETRONIC tetra-functional block copolymers basedon ethylene oxide and propylene oxide, such as TETRONIC R, which arecommercially available from BASF Corp. of Parsippany, N.J.

As used herein, the phrase “polyether polyols” also can includepoly(oxytetramethylene) diols prepared by the polymerization oftetrahydrofuran in the presence of Lewis acid catalysts such as but notlimited to boron trifluoride, tin (IV) chloride and sulfonyl chloride.

Group D

In some non-limiting embodiments, the present invention providespolyurethanes of Group D comprising a reaction product of componentscomprising: at least one polyisocyanate; at least one branched polyolhaving 4 to 18 carbon atoms and at least 3 hydroxyl groups; and at leastone polyol having one or more bromine atoms, one or more phosphorusatoms or combinations thereof. Brominated or phosphonated polyols canprovide the polyurethane with enhanced flame retardancy. The flameretardancy of polyurethanes of the present invention can be determinedsimply by exposure to flame to determine if the polymer isself-extinguishing or burns more slowly that a polymer without thebrominated or phosphonated polyol, or according to Underwriter'sLaboratory Test UL-94.

In other non-limiting embodiments, the present invention providespolyurethanes of Group D comprising a reaction product of componentsconsisting of: about 1 equivalent of 4,4′-methylene-bis-(cyclohexylisocyanate); about 0.3 to about 0.5 equivalents of trimethylolpropane;about 0.2 to about 0.5 equivalents ofbis(4-(2-hydroxyethoxy)-3,5-dibromophenyl)sulfone; about 0.2 to about0.5 equivalents of 1,4-cyclohexane dimethanol; and about 0.2 to about0.5 equivalents of 3,6-dithia-1,2-octanediol.

Non-limiting examples of suitable polyisocyanates and branched polyolshaving 4 to 18 carbon atoms and at least 3 hydroxyl groups for use in asreaction products for preparing the polyurethanes of Group D arediscussed in detail above with respect to Group A.

Non-limiting examples of suitable polyols having one or more bromineatoms, one or more phosphorus atoms or combinations thereof include4,4′-isopropylidene bis(2,6-dibromophenol), isopropylidenebis[2-(2,6-dibromo-phenoxy)ethanol],bis(4-(2-hydroxyethoxy)-3,5-dibromophenyl)sulfone heptakis(dipropyleneglycol)triphosphite, tris(dipropylene glycol)phosphate,diethyl-N,N-bis(2-hydroxyethyl)aminoethanol phosphonate and mixturesthereof. Non-limiting examples of suitable phosphonated polyols includethose of the formula HO—Y—O[POOR-O—Y—O][POOR-O—Y—OH, wherein each R isindependently selected from an alkylene group having 1 to 10 repeatunits, such as CH₂ to (CH₂)₁₀ and each Y is independently selected froman alkylene group having 1 to 6 repeat units, such as CH₂ to (CH₂)₆.

The amount of brominated polyols and/or phosphonated polyols used toform the polyurethane of Group D can be about 0.1 to about 0.9equivalents, or about 0.3 to about 0.9 equivalents, or about 0.3equivalents.

In some non-limiting embodiments, the reaction components can furthercomprise one or more of the polyether polyols and/or polyester polyolsdiscussed above. If present, the amount of polyether polyols and/orpolyester polyols used to form the polyurethane of Group D can be about0.1 to about 0.9 equivalents, or about 0.3 to about 0.9 equivalents, orabout 0.3 equivalents.

Groups A-D

In some non-limiting embodiments of the polyurethanes of Groups A-D, thereaction products can further comprise one or more of the following:polyurethane polyols, (meth)acrylamides, hydroxy(meth)acrylamides,polyvinyl alcohols, polymers containing hydroxy functional(meth)acrylates, polymers containing allyl alcohols, polyesteramides andmixtures thereof. In some embodiments, polymerization with acrylamidescan form an interpenetrating network having high transparency, goodimpact strength, and high Young's modulus.

Non-limiting examples of suitable polyurethane polyols include thereaction product of an excess of polyisocyanate and a branched orstraight chain polyol. The equivalent ratio of polyisocyanate to polyolcan range from about 1.0:0.05 to about 1.0.3, or about 1.0:0.7. Theamount of polyurethane polyols used can range from about 1 to about 90weight percent, about 5 to about 70 weight percent, or about 20 to about50 weight percent on a basis of total weight of the components.

Non-limiting examples of suitable acrylamides include acrylamide,methacrylamide and dimethylacrylamide. The acrylamide can be added withall of the other reaction components, or it can be dissolved in the dioland then mixed with the other reaction components. The amount ofacrylamide used can range from about 5 to about 70 weight percent, about10 to about 50 weight percent, or about 10 to about 30 weight percent ona basis of total weight of the components.

Non-limiting examples of suitable polyvinyl alcohols include polyvinylalcohol. The amount of polyvinyl alcohol used can range from about 5 toabout 90 weight percent, about 10 to about 70 weight percent, or about10 to about 40 weight percent on a basis of total weight of thecomponents.

Non-limiting examples of suitable polymers containing hydroxy functional(meth)acrylates include hydroxypropylacrylate; hydroxyethylacrylate;hydroxypropylmethacrylate; hydroxyethylmethacrylate; and copolymers ofhydroxy functional (meth)acrylates with acrylamides,cyanoethyl(meth)acrylates, methylmethacrylates, methacrylates,ethacrylates, propylacrylates and vinylpyrrolidinone. The amount ofhydroxy functional (meth)acrylates used can range from about 10 to about90 weight percent, about 10 to about 70 weight percent, or about 10 toabout 30 weight percent on a basis of total weight of the components.

Non-limiting examples of suitable polymers containing allyl alcoholsinclude diethylene glycol bis(allylcarbonate), allyloxytrimethylsilane,and diallylcarbonate. The amount of allyl alcohols used can range fromabout 5 to about 70 weight percent, about 10 to about 50 weight percent,or about 10 to about 30 weight percent.

Non-limiting examples of suitable polyesteramides include esteramidepolymers obtained by the reaction of bis-oxamidodiols such asN,N′-bis(omega-hydroxyalkylene)oxamide with a dicarboxylic acid ordiester such as diethyl oxalate, diethyl succinates, diethyl suberate,or dimethyl terephthalate. The amount of polyesteramides used can rangefrom about 10 to about 80 weight percent, about 20 to about 60 weightpercent, or about 30 to about 50 weight percent on a basis of totalweight of the components.

In some non-limiting embodiments of the polyurethanes of Groups A-C, thereaction products can further comprise one or more amine curing agents.The amine curing agent, if present, can act as a catalyst in thepolymerization reaction, be incorporated into the resulting polymerizateand can form poly(ureaurethane)s. The amount of amine curing agent usedcan range from about 0.05 to about 0.9 equivalents, about 0.1 to about0.7 equivalents, or about 0.3 to about 0.5 equivalents.

Non-limiting examples of such amine curing agents include aliphaticpolyamines, cycloaliphatic polyamines, aromatic polyamines and mixturesthereof. In some non-limiting embodiments, the amine curing agent canhave at least two functional groups selected from primary amine (—NH₂),secondary amine (—NH—) and combinations thereof. In some non-limitingembodiments, the amine curing agent can have at least two primary aminegroups. In some non-limiting embodiments, the amino groups are allprimary groups.

Examples of such amine curing agents include compounds having thefollowing formula:

wherein R₁ and R₂ are each independently selected from methyl, ethyl,propyl, and isopropyl groups, and R₃ is selected from hydrogen andchlorine, such as the following compounds manufactured by Lonza Ltd.(Basel, Switzerland): LONZACURE® M-DIPA, in which R₁═C₃ H₇; R₂═C₃ H₇;R₃═H; LONZACURE® M-DMA, in which R₁═CH₃; R₂═CH₃; R₃═H; LONZACURE® M-MEA,in which R₁═CH₃; R₂═C₂ H₅; R₃═H; LONZACURE® M-DEA, in which R₁═C₂ H₅;R₂═C₂ H₅; R₃═H; LONZACURE® M-MIPA,: in which R₁═CH₃; R₂═C₃ H₇; R₃═H; andLONZACURE® M-CDEA, in which R₁═C₂ H₅; R₂═C₂ H₅; R₃═Cl, each of which iscommercially available from Air Products and Chemicals, Inc. ofAllentown, Pa.

Such amine curing agents can include a diamine curing agent such as4,4′-methylenebis(3-chloro-2,6-diethylaniline), (LONZACURE® M-CDEA);2,4-diamino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene andmixtures thereof (collectively “diethyltoluenediamine” or “DETDA”),which is commercially available from Albemarle Corporation under thetrade name ETHACURE 100; dimethylthiotoluenediamine (DMTDA)(commercially available as ETHACURE 300); the color stabilized versionof ETHACURE 100 (i.e., formulation which contains an additive to reduceyellow color), which is available under the name ETHACURE 100S;4,4′-methylene-bis-(2-chloroaniline) (commercially available fromKingyorker Chemicals under the trade name MOCA). DETDA can be a liquidat room temperature with a viscosity of 156 centipoise (cp) at 25° C.DETDA can be isomeric, with the 2,4-isomer amount being from 75 to 81percent while the 2,6-isomer amount can be from 18 to 24 percent.

Other non-limiting examples of amine curing agents includeethyleneamines, such as ethylenediamine (EDA), diethylenetriamine(DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA),pentaethylenehexamine (PEHA), piperazine, morpholine, substitutedmorpholine, piperidine, substituted piperidine, diethylenediamine(DEDA), and 2-amino-1-ethylpiperazine. In some non-limiting embodiments,the amine curing agent can be selected from one or more isomers of C₁-C₃dialkyl toluenediamine, such as 3,5-dimethyl-2,4-toluenediamine,3,5-dimethyl-2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine,3,5-diethyl-2,6-toluenediamine, 3,5-diisopropyl-2,4-toluenediamine,3,5-diisopropyl-2,6-toluenediamine, and mixtures thereof. In somenon-limiting embodiments, the amine curing agent can be methylenedianiline or trimethyleneglycol di(para-aminobenzoate).

Other non-limiting examples of amine curing agents include compounds ofthe following general structures (XIII-XV):

Other non-limiting examples of amine curing agents include one or moremethylene bis anilines represented by the general formulas XVI-XX, oneor more aniline sulfides represented by the general formulas XXI-XXV,and/or one or more bianilines represented by the general formulasXXVI-XXVIX,

wherein R₃ and R4 are each independently C₁-C₃ alkyl, and R₅ is selectedfrom hydrogen and halogen, such as chlorine or bromine. The diaminerepresented by general formula XV can be described generally as a4,4′-methylene-bis(dialkylaniline). Suitable non-limiting examples ofdiamines which can be represented by general formula XV include but arenot limited to 4,4′-methylene-bis(2,6-dimethylaniline),4,4′-methylene-bis(2,6-diethylaniline),4,4′-methylene-bis(2-ethyl-6-methylaniline),4,4′-methylene-bis(2,6-diisopropylaniline),4,4′-methylene-bis(2-isopropyl-6-methylaniline) and4,4′-methylene-bis(2,6-diethyl-3-chloroaniline).

The amine curing agent includes compounds represented by the followinggeneral structure (XXX):

where R₂₀, R₂₁, R₂₂, and R₂₃ are each independently selected from H,C₁-C₃ alkyl, CH₃—S— and halogen, such as chlorine or bromine. The aminecuring agent represented by general formula XXX can include diethyltoluene diamine (DETDA) wherein R₂₃ is methyl, R₂₀ and R₂₁ are eachethyl and R₂₂ is hydrogen. Also, the amine curing agent can include4,4′-methylenedianiline.

In an embodiment wherein it is desirable to produce a poly(ureaurethane)having low color, the amine curing agent can be selected such that ithas relatively low color and/or it can be manufactured and/or stored ina manner as to prevent the amine from developing a color (e.g., yellow).

In some non-limiting embodiments of the polyurethanes of Groups A-D, thereaction products can be essentially free of amine curing agent. As usedherein, “essentially free of amine curing agent” means that the reactionproduct components comprise less than about 10 weight percent of aminecuring agent, or less than about 5 weight percent of amine curing agent,or less than about 2 weight percent of amine curing agent, or in othernon-limiting embodiments are free of amine curing agent.

Group E

In some non-limiting embodiments, the. present invention providespolyurethanes of Group E comprising a reaction product of componentscomprising: about 1 equivalent of at least one polyisocyanate; about 0.3to about 1 equivalents of at least one branched polyol having 4 to 18carbon atoms and at least 3 hydroxyl groups; and about 0.01 to about 0.3equivalents of at least one polycarbonate diol, wherein the reactionproduct components are essentially free of polyether polyol and aminecuring agent and wherein the reaction components are maintained at atemperature of at least about 100° C. for at least about 10 minutes.

Non-limiting examples of suitable polyisocyanates, branched polyolshaving 4 to 18 carbon atoms and at least 3 hydroxyl groups,polycarbonate diols and diol having 2 to 18 carbon atoms for use in asreaction products for preparing the polyurethanes of Group E arediscussed in detail above with respect to Group A.

In some non-limiting embodiments, the amount of branched polyol used toform the polyurethane of Group E can range from about 0.3 to about 0.98equivalents, or about 0.5 to about 0.98 equivalents, or about 0.3equivalents or about 0.9 to about 0.98 equivalents.

In some non-limiting embodiments, the amount of polycarbonate diol usedto form the polyurethane of Group E can range from about 0.01 to about0.1 equivalents, or about 0.05 to about 0.1 equivalents, or about 0.1equivalents.

In another embodiment, the present invention provides polyurethanes ofGroup E comprising a reaction product of components consisting of: about1 equivalent of 4,4′-methylene-bis-(cyclohexyl isocyanate); about 0.3equivalents of trimethylolpropane; about 0.55 equivalents of1,5-pentanediol and about 0.15 equivalents of KM10-1733 polycarbonatediol prepared from hexanediol, available from Stahl, wherein thereaction components are maintained at a temperature of at least about100° C. for at least about 10 minutes.

In another embodiment, the present invention provides polyurethanes ofGroup E comprising a reaction product of components consisting of: about1 equivalent of 4,4′-methylene-bis-(cyclohexyl isocyanate); about 0.3equivalents of trimethylolpropane; about 0.5 equivalents of1,5-pentanediol and about 0.2 equivalents of KM10-1733 polycarbonatediol prepared from hexanediol, available from Stahl, wherein thereaction components are maintained at a temperature of at least about100° C. for at least about 10 minutes.

The polyurethanes of Group E can exhibit good ballistics resistance.

The polyurethanes of Group E are essentially free of polyether polyoland amine curing agent, the types and amounts of polyether polyol andamine curing agent being described above with respect to Groups A-D.

In some non-limiting embodiments of the polyurethanes of Group E, thereaction products can further comprise one or more of the following:polyurethane polyols, acrylamides, polyvinyl alcohols, polymerscontaining hydroxy functional (meth)acrylates, polymers containing allylalcohols, polyesteramides and mixtures thereof, as described and inamounts as above with respect to Groups A-D.

Group F

In some non-limiting embodiments, the present invention providespolyurethanes of Group F comprising a reaction product of componentscomprising: (a) about 1 equivalent of at least one polyisocyanate; (b)about 0.3 to about 1 equivalents of at least one branched polyol having4 to 18 carbon atoms and at least 3 hydroxyl groups; (c) about 0.01 toabout 0.3 equivalents of at least one polycarbonate diol; and (d) about0.1 to about 0.9 equivalents of at least one diol having 2 to 18 carbonatoms, wherein the reaction product components are essentially free ofpolyether polyol and wherein the reaction components are maintained at atemperature of at least about 100° C. for at least about 10 minutes. Thediol having 2 to 18 carbon atoms is chemically different from thepolycarbonate diol, e.g., the diol has at least one different atom or adifferent arrangement of atoms compared to the polycarbonate diol.

Non-limiting examples of suitable polyisocyanates, branched polyolshaving 4 to 18 carbon atoms and at least 3 hydroxyl groups,polycarbonate diols and diol having 2 to 18 carbon atoms for use in asreaction products for preparing the polyurethanes of Group F arediscussed in detail above with respect to Group A.

In some non-limiting embodiments, the amount of branched polyol used toform the polyurethane of Group F can range from about 0.3 to about 0.98equivalents, or about 0.5 to about 0.98 equivalents, or about 0.9 toabout 0.98 equivalents.

In some non-limiting embodiments, the amount of polycarbonate diol usedto form the polyurethane of Group F can range from about 0.01 to about0.1 equivalents, or about 0.05 to about 0.1 equivalents, or about 0.1equivalents.

In some non-limiting embodiments, the amount of diol used to form thepolyurethane of Group F can range from about 0.01 to about 0.1equivalents, or about 0.05 to about 0.1 equivalents, or about 0.1equivalents.

The polyurethanes of Group F are essentially free of polyether polyol,the types and amounts of polyether polyol being described above withrespect to Groups A-D.

In some non-limiting embodiments of the polyurethanes of Group F, thereaction products can further comprise one or more of the following:polyurethane polyols, acrylamides, polyvinyl alcohols, polymerscontaining hydroxy functional (meth)acrylates, polymers containing allylalcohols, polyesteramides and mixtures thereof, as described and inamounts as above with respect to Groups A-D.

In some non-limiting embodiments of the polyurethanes of Group F, thereaction products can further comprise one or more amine curing agentsas discussed above with respect to Group E. In other non-limitingembodiments, the reaction products for preparing the polyurethanes ofGroup F can be essentially free of or free of amine curing agent asdiscussed above with respect to Groups A-D.

Group G

In some non-limiting embodiments, the present invention providespolyurethanes of Group G comprising a reaction product of componentscomprising: about 1 equivalent of at least one polyisocyanate; about 0.3to about 1 equivalents of at least one branched polyol having 4 to 18carbon atoms and at least 3 hydroxyl groups; about 0.01 to about 0.3equivalents of at least one polyol selected from the group consisting ofpolyester polyol, polycaprolactone polyol and mixtures thereof; andabout 0.1 to about 0.7 equivalents of at least one aliphatic diol,wherein the reaction product components are essentially free ofpolyether polyol and amine curing agent and wherein the reactioncomponents are maintained at a temperature of at least about 100° C. forat least about 10 minutes, wherein the reaction components aremaintained at a temperature of at least about 100° C. for at least about10 minutes.

Non-limiting examples of suitable polyisocyanates, branched polyolshaving 4 to 18 carbon atoms and at least 3 hydroxyl groups, polyesterpolyols, polycaprolactone polyols and aliphatic diols for use asreaction products for preparing the polyurethanes of Group G arediscussed in detail above with respect to Group A. The aliphatic diol ischemically different from the polyester polyol and polycaprolactonepolyol, e.g., the diol has at least one different atom or a differentarrangement of atoms compared to the polyester polyol andpolycaprolactone polyol.

In some non-limiting embodiments, the amount of branched polyol used toform the polyurethane of Group G can range from about 0.3 to about 0.9equivalents, or about 0.3 to about 0.7 equivalents, or about 0.4equivalents to about 0.6 equivalent, or about 0.7 equivalents.

In some non-limiting embodiments, the amount of polyester and/orpolycaprolactone polyol used to form the polyurethane of Group GF canrange from about 0.01 to about 0.1 equivalents, or about 0.05 to about0.1 equivalents, or about 0.1 equivalents.

In some non-limiting embodiments, the amount of aliphatic diol used toform the polyurethane of Group G can range from about 0.1 to about 0.6equivalents, or about 0.1 to about 0.5 equivalents, or about 0.5equivalents.

The polyurethanes of Group G are essentially free of or free ofpolyether polyol and/or amine curing agent, the types and amounts ofpolyether polyol and amine curing agent being described above withrespect to Groups A-D.

In some non-limiting embodiments of the polyurethanes of Group G, thereaction products can further comprise one or more of the following:polyurethane polyols, acrylamides, polyvinyl alcohols, polymerscontaining hydroxy functional (meth)acrylates, polymers containing allylalcohols, polyesteramides and mixtures thereof, as described and inamounts as above with respect to Groups A-D.

In other non-limiting embodiments, the present invention providespolyurethanes of Group G comprising a reaction product of componentsconsisting of: about 1 equivalent of 4,4′-methylene-bis-(cyclohexylisocyanate); about 0.3 equivalents of trimethylolpropane; about 0.5equivalents of decanediol; and about 0.2 equivalents of polycaprolactonepolyol, such as Dow TONE 0210 polycaprolactone polyol having a numberaverage molecular weight of about 1000 grams/mole, wherein the reactioncomponents are maintained at a temperature of at least about 100° C. forat least about 10 minutes.

In other non-limiting embodiments, the present invention providespolyurethanes of Group G prepared from a prepolymer which is thereaction product of components comprising: (1) about 0.4 equivalents of4,4′-methylene-bis-(cyclohexyl isocyanate) (such as DESMODUR W); (2)about 0.3 equivalents of polycaprolactone diol (such as CAPA 2047 andCAPA 2077A polycaprolactone diols prepared from hexanediol); (3) about0.05 equivalents of trimethylolpropane. The prepolymer is reacted withat least one aliphatic diol having 2 to 18 carbon atoms as describedabove, such as butanediol or pentanediol.

Group H

In other non-limiting embodiments, the present invention providespolyurethanes of Group H comprising a reaction product of componentscomprising: (a) a prepolymer which is the reaction product of componentscomprising: (1) at least one polyisocyanate; (2) at least onepolycaprolactone polyol; and (3) at least one polyol selected from thegroup consisting of polyalkylene polyol, polyether polyol and mixturesthereof; and (b) at least one diol having 2 to 18 carbon atoms.

Non-limiting examples of suitable polyisocyanates, polycaprolactonepolyols, polyalkylene polyols, polyether polyols and diols having 2 to18 carbon atoms for use as reaction products for preparing thepolyurethanes of Group H are discussed in detail above with respect toGroup A. Non-limiting examples of suitable polyalkylene polyols includepolyethylene glycols, polypropylene glycols and mixtures thereof. Thepolyalkylene glycol can have a number average molecular weight rangingfrom about 200 to about 1000 grams/mole, or from about 200 grams/mole toabout 4,000 grams/mole.

The diol is chemically different from the polyalkylene polyol andpolyether polyol, e.g., the diol has at least one different atom or adifferent arrangement of atoms compared to the polyalkylene polyol andpolyether polyol.

In some non-limiting embodiments, the amount of branchedpolycaprolactone polyol used to form the polyurethane of Group H canrange from about 0.05 to about 0.8 equivalents, or about 0.1 to about0.6 equivalents, or about 0.1 equivalents to about 0.4 equivalent, orabout 0.3 equivalents.

In some non-limiting embodiments, the amount of polyalkylene polyoland/or polyether polyol used to form the polyurethane of Group H canrange from about 0.1 to about 0.9 equivalents, or about 0.2 to about 0.6equivalents, or about 0.4 equivalents.

In some non-limiting embodiments, the amount of diol used to form thepolyurethane of Group H can range from about 0.1 to about 0.9equivalents, or about 0.3 to about 0.8 equivalents, or about 0.7equivalents.

The polyurethanes of Group H are prepared by reacting reaction productcomponents comprising: (1) at least one polyisocyanate; (2) at least onepolycaprolactone polyol; and (3) at least one polyol selected from thegroup consisting of polyalkylene polyol, polyether polyol and mixturesthereof to form a prepolymer. The prepolymer is then reacted with atleast one diol having 2 to 18 carbon atoms and any other optionalreaction components as described below.

In some non-limiting embodiments of the polyurethanes of Group H, thereaction products can further comprise one or more of the following:branched polyols having at lest three hydroxyl groups, polyurethanepolyols, acrylamides, polyvinyl alcohols, polymers containing hydroxyfunctional (meth)acrylates, polymers containing allyl alcohols,polyesteramides and mixtures thereof, as described and in amounts asabove with respect to Groups A-D.

In some non-limiting embodiments of the polyurethanes of Group H, thereaction products can further comprise one or more amine curing agentsas discussed above with respect to Group E. In other non-limitingembodiments, the reaction products for preparing the polyurethanes ofGroup H can be essentially free of or free of amine curing agent asdiscussed above with respect to Groups A-D.

In other non-limiting embodiments, the present invention providespolyurethanes of Group H comprising a reaction product of componentscomprising: (a) a prepolymer which is the reaction product of componentscomprising: (1) aliphatic or cycloaliphatic diisocyanate; (2)polycaprolactone diol; (3) polyethylene glycol; and (4) polyoxyethyleneand polyoxypropylene copolymer and (b) at least one diol having 2 to 18carbon atoms.

In other non-limiting embodiments, the present invention providespolyurethanes of Group H prepared from a prepolymer which is thereaction product of components comprising: (1) about 0.4 equivalents of4,4′-methylene-bis-(cyclohexyl isocyanate) (such as DESMODUR W); (2)about 0.003 equivalents of polycaprolactone diol (such as CAPA 2077Apolycaprolactone diol prepared from hexanediol); (3) about 0.025equivalents of polyethylene glycol (such as PLURACOL E400NF); (4) about0.029 equivalents of polyoxyethylene and polyoxypropylene copolymer(such as PLURONIC L62D ethylene oxide/propylene oxide block copolymer);(5) about 0.05 equivalents of trimethylolpropane; and additives such ascatalyst (for example dibutyltin dilaurate), antioxidant (such asIRGANOX 1010 and IRGANOX MD 1024), and ultraviolet light stabilizer(s)such as CYASORB UV 5411 and TINUVIN 328 (each described below).

The isocyanate-terminated prepolymer is reacted with at least one diolhaving 2 to 18 carbon atoms, such as 1,4-butanediol and/or1,4-cyclohexane dimethanol in an equivalent ratio of about 0.75:0.251,4-butanediol to 1,4-cyclohexane dimethanol. The equivalent ratio ofprepolymer to diol is about 1:1.

Groups A-H

Referring now to the inventions of Groups A-H, the polyurethanes of thepresent invention can be polymerized using a variety of techniques. Insome non-limiting embodiments described in further detail below,polyisocyanate and polyol can be reacted together in a one-pot processto form the polyurethane. Sulfur-containing polyurethanes of the presentinvention can be produced by combining isocyanate and/or isothiocyanateand polyol and/or polythiol.

In other non-limiting embodiments, the polyurethane can be prepared byreacting polyisocyanate(s) and polyol(s) to form a polyurethaneprepolymer and then introducing diol(s), and optionally catalyst andother optional reaction components.

In other non-limiting embodiments such as Group B, the polyurethane canbe prepared by reacting polyisocyanate(s) and diol(s) to form anisocyanate functional urethane prepolymer and then introducing diol(s),polyols and optionally catalyst and other optional reaction components.In some embodiments, the isocyanate functional urethane prepolymer,polyol and second portion of diol reaction components are maintained ata temperature of at least about 100° C. for at least about 10 minutes,or at least about 110° C. for at least about 10 minutes or 20 minutes.

Whether prepared in a one-shot process or in a multi-stage process usinga prepolymer, in some non-limiting embodiments, the aforementionedingredients each can be degassed prior to reaction. In some non-limitingembodiments, the prepolymer can be degassed, the difunctional materialcan be degassed, and then these two materials can be combined.

In the “one shot” or bulk polymerization method, all of the ingredients,that is, isocyanate, polyol and diol are mixed simultaneously. Thismethod is generally satisfactory when all active hydrogens react atabout the same rate such as when all contain hydroxyl groups as the onlyreactive sites. The urethane reaction can be conducted under anhydrousconditions with dry reactants such as in a nitrogen atmosphere ofatmospheric pressure and at a temperature ranging from about 75° C. toabout 140° C. If polycarbonate polyols or any hydroxy functionalcompounds are used, they are typically dried before reaction, usually toa moisture content ranging from about 0.01 to about 0.05 percent.

To obtain the randomness desired and a generally clear polymer, thediol, for example, anhydrous 1,4-butanediol (containing a maximum of0.04 percent water) can be added to the polyol under a nitrogenatmosphere to exclude moisture and the temperature maintainedsufficiently high so that there is no phase separation and a homogeneousmixture is obtained. The polyisocyanate, for example,4,4′-methylene-bis-(cyclohexyl isocyanate), can be added rapidly and themixture can be maintained at a temperature of at least about 75° C., orat least about 85° C., or at least about 90° C., or at least about 95°C. for at least about 10 minutes or at least about 20 minutes. In someembodiments, the mixture is maintained at a temperature of at leastabout 100° C., or at least about 105° C., or at least about 110° C. forat least about 10 minutes or at least about 20 minutes, so that there isno phase separation and the mixture remains homogeneous. The mixture canbe maintained at a pressure of ranging from about 2 to about 6 mm Hg(about 266.6 to about 800 Pascal (Pa)), or about 266.6 Pa for a timeperiod of about 10 minutes to about 24 hours, or about 10 minutes toabout 4 hours.

In some non-limiting embodiments, the mixture can be vigorously agitatedat a temperature of at least about 75° C., or at least about 85° C., orat least about 90° C., or at least about 95° C., or at least about 100°C., or at least about 105° C., or at least about 110° C., and degassedfor a period of at least about 3 minutes during which time the pressureis reduced from atmospheric to about 3 millimeters of mercury. Thereduction in pressure facilitates the removal of the dissolved gasessuch as nitrogen and carbon dioxide and then the ingredients can bereacted at a temperature ranging from about 100° C. to about 140° C., orabout 110° C. to about 140° C., in the presence of a catalyst and thereaction continued until there are substantially no isocyanate groupspresent, in some embodiments for at least about 6 hours. In the absenceof a catalyst, the reaction can be conducted for at least about 24hours, such as under a nitrogen atmosphere.

In some non-limiting embodiments, wherein a window can be formed, thepolymerizable mixture which can be optionally degassed can be introducedinto a mold and the mold can be heated (i.e., thermal cure cycle) usinga variety of conventional techniques known in the art. The thermal curecycle can vary depending on the reactivity and molar ratio of thereactants. In a non-limiting embodiment, the thermal cure cycle caninclude heating the mixture of prepolymer and diol and optionally dioland dithiol; or heating the mixture of polyisocyanate, polyol and/orpolythiol and diol or diol/dithiol, from room temperature to atemperature of about 200° C. over a period of from about 0.5 hours toabout 72 hours; or from about 80° C. to about 150° C. for a period offrom about 5 hours to about 48 hours.

In other non-limiting embodiments described in further detail below,isocyanate and polyol can be reacted together to form a polyurethaneprepolymer and the prepolymer can be reacted with more of the same or adifferent polyol(s) and/or diol(s) to form a polyurethane orsulfur-containing polyurethane. When the prepolymer method is employed,the prepolymer and diol(s) can be heated so as to reduce the prepolymerviscosity to about 200 cp or at most a few thousand centipoise so as toaid in mixing. As in the bulk polymerization, reaction should beconducted under anhydrous conditions with dry reactants.

The polyurethane prepolymer can have a number average molecular weight(Mn) of less than about 50,000 grams/mole, or less than about 20,000grams/mole, or less than about 10,000 grams/mole, or less than about5,000 grams/mole, or at least about 1,000 grams/mole or at least about2,000 grams/mole, inclusive of any range in between.

When polyurethane-forming components, such as polyols and isocyanates,are combined to produce polyurethanes, the relative amounts of theingredients are typically expressed as a ratio of the available numberof reactive isocyanate groups to the available number of reactivehydroxyl groups, i.e., an equivalent ratio of NCO:OH. For example, aratio of NCO:OH of 1.0:1.0 is obtained when the weight of one NCOequivalent of the supplied form of the isocyanate component is reactedwith the weight of one OH equivalent of the supplied form of the organicpolyol component. The polyurethanes of the present invention can have anequivalent ratio of NCO:OH ranging from about 0.9:1.0 to about 1.1:1.0,or about 1.0:1.0.

In some non-limiting embodiments, when the isocyanate and polyol arereacted to form a prepolymer, the isocyanate is present in excess, forexample the amount of isocyanate and the amount of polyol in theisocyanate prepolymer can be selected such that the equivalent ratio of(NCO):(OH) can range from about 1.0: 0.05 to about 1.0:0.7.

In some non-limiting embodiments, the amount of isocyanate and theamount of polyol used to prepare isocyanate-terminated polyurethaneprepolymer or isocyanate-terminated sulfur-containing polyurethaneprepolymer can be selected such that the equivalent ratio of(NCO):(SH+OH) can be at least about 1.0:1.0, or at least about 2.0:1.0,or at least about 2.5:1.0, or less than about 4.5:1.0, or less thanabout 5.5:1.0; or the amount of isothiocyanate and the amount of polyolused to prepare isothiocyanate-terminated sulfur-containing polyurethaneprepolymer can be selected such that the equivalent ratio of(NCS):(SH+OH) can be at least about 1.0:1.0, or at least about 2.0:1.0,or at least about 2.5:1.0, or less than about 4.5:1.0, or less thanabout 5.5:1.0; or the amount of a combination of isothiocyanate andisocyanate and the amount of polyol used to prepareisothiocyanate/isocyanate terminated sulfur-containing polyurethaneprepolymer can be selected such that the equivalent ratio of(NCS+NCO):(SH+OH) can be at least about 1.0:1.0, or at least about2.0:1.0, or at least about 2.5:1.0, or less than about 4.5:1.0, or lessthan about 5.5:1.0

The ratio and proportions of the diol and the polyol can affect theviscosity of the prepolymer. The viscosity of such prepolymers can beimportant, for example when they are intended for use with coatingcompositions, such as those for flow coating processes. The solidscontent of such prepolymers, however, also can be important, in thathigher solids content can achieve desired properties from the coating,such as weatherability, scratch resistance, etc. In conventionalcoatings, coating compositions with higher solids content typicallyrequire greater amounts of solvent material to dilute the coating inorder to reduce the viscosity for appropriate flow coating processes.The use of such solvents, however, can adversely affect the substratesurface, particularly when the substrate surface is a polymericmaterial. In the present invention, the viscosity of the prepolymer canbe appropriately tailored to provide a material with lower viscositylevels at higher solids content, thereby providing an effective coatingwithout the need for excessive amounts of solvents which candeleteriously affect the substrate surface.

In some non-limiting embodiments in which optional amine curing agent isused, the amount of isocyanate-terminated polyurethane prepolymer orsulfur-containing isocyanate-terminated polyurethane prepolymer and theamount of amine curing agent used to prepare sulfur-containingpolyurethane can be selected such that the equivalent ratio of(NH+SH+OH):(NCO) can range from about 0.80:1.0 to about 1.1:1.0, or fromabout 0.85:1.0 to about 1.0:1.0, or from about 0.90:1.0 to about1.0:1.0, or from about 0.90:1.0 to about 0.95:1.0, or from about0.95:1.0 to about 1.0:1.0.

In some non-limiting embodiments, the amount of isothiocyanate orisothiocyanate/isocyanate terminated sulfur-containing polyurethaneprepolymer and the amount of amine curing agent used to preparesulfur-containing polyureaurethane can be selected such that theequivalent ratio of (NH+SH+OH):(NCO+NCS) can range from about 0.80:1.0to about 1.1:1.0, or from about 0.85:1.0 to about 1.0:1.0, or from about0.90:1.0 to about 1.0:1.0, or from about 0.90:1.0 to about 0.95:1.0, orfrom about 0.95:1.0 to about 1.0:1.0.

It is believed that the unusual energy absorption properties andtransparency of the polyurethanes of the present invention may not onlybe dependent upon the urethane ingredients and proportions, but also maybe dependent on the method of preparation. More particularly, it isbelieved that the presence of polyurethane regular block segments mayadversely affect the polyurethane transparency and energy absorptionproperties and consequently it is believed that random segments withinthe polymer can provide optimal results. Consequently, whether theurethane contains random or regular block segments depends upon theparticular reagents and their relative reactivity as well as theconditions of reaction. Generally speaking, the polyisocyanate will bemore reactive with a low molecular weight diol or polyol, for example,1,4-butanediol, than with a polymeric polyol and, hence, in somenon-limiting embodiments it is desirable to inhibit the preferentialreaction between the low molecular weight diol or polyol and thepolyisocyanate such as by rapidly adding the polyisocyanate to anintimate mixture of the low molecular weight diol or polyol andpolymeric polyol with vigorous agitation, such as at a temperature of atleast about 75° C. when no catalyst is employed, and then maintained attemperature of reaction of at least about 100° C. or about 110° C. afterthe exotherm has subsided. When a catalyst is employed, the initialmixing temperature can be lower, such as about 60° C., so that theexotherm does not carry the temperature of the mixture substantiallyabove the reaction temperature desired. Inasmuch as the polyurethanesare thermally stable, however, reaction temperatures can reach as highas about 200° C. and as low as about 60° C., and in some non-limitingembodiments ranging from about 75° C. to about 130° C. when a catalystis employed, or ranging from about 80° C. to about 100° C. When nocatalyst is employed, in some non-limiting embodiments the reactiontemperature can range from about 130° C. to about 150° C.

It is also desirable to rapidly attain reaction temperatures after ahomogeneous mixture is obtained when a catalyst is not employed, so thatthe polymer does not become hazy due to phase separation. For example,some mixtures can become hazy in less than one-half hour at less than80° C. without catalyst. Thus, it can be desirable either to use acatalyst or introduce the reactants to rapidly reach a reactiontemperature above about 100° C., or about 110° C. or about 130° C., forexample by the use of a high-speed shear mixing head, so that thepolymer does not become hazy. Suitable catalysts can be selected fromthose known in the art. In some non-limiting embodiments, degassing cantake place prior to or following addition of catalyst.

In some non-limiting embodiments, a urethane-forming catalyst can beused in the present invention to enhance the reaction of thepolyurethane-forming materials. Suitable urethane-forming catalystsinclude those catalysts that are useful for the formation of urethane byreaction of the NCO and OH-containing materials, and which have littletendency to accelerate side reactions leading to allophonate andisocyanate formation. Non-limiting examples of suitable catalysts areselected from the group of Lewis bases, Lewis acids and insertioncatalysts as described in Ullmann's EncycloDedia of IndustrialChemistry, 5^(th) Edition, 1992, Volume A21, pp. 673 to 674.

In some non-limiting embodiments, the catalyst can be a stannous salt ofan organic acid, such as stannous octoate or butyl stannoic acid. Othernon-limiting examples of suitable catalysts include tertiary aminecatalysts, tertiary ammonium salts, tin catalysts, phosphines ormixtures thereof. In some non-limiting embodiments, the catalysts can bedimethyl cyclohexylamine, dibutyl tin dilaurate, dibutyltin diacetate,dibutyltin mercaptide, dibutyltin diacetate, dibutyl tin dimaleate,dimethyl tin diacetate, dimethyl tin dilaurate,1,4-diazabicyclo[2.2.2]octane, bismuth carboxylates, zirconiumcarboxylates, zinc octoate, ferric acetylacetonate and mixtures thereof.The amount of catalyst used can vary depending on the amount ofcomponents, for example about 10 ppm to about 600 ppm.

In alternate non-limiting embodiments, various additives can be includedin compositions comprising the polyurethane(s) of the present invention.Such additives include light stabilizers, heat stabilizers,antioxidants, colorants, fire retardants, ultraviolet light absorbers,light stabilizers such as hindered amine light stabilizers, mold releaseagents, static (non-photochromic) dyes, fluorescent agents, pigments,surfactants, flexibilizing additives, such as but not limited toalkoxylated phenol benzoates and poly(alkylene glycol)dibenzoates, andmixtures thereof. Non-limiting examples of anti-yellowing additivesinclude 3-methyl-2-butenol, organo pyrocarbonates and triphenylphosphite (CAS Registry No. 101-02-0). Examples of useful antioxidantsinclude IRGANOX 1010, IRGANOX 1076, and IRGANOX MD 1024, eachcommercially available from Ciba Specialty Chemicals of Tarrytown, N.Y.Examples of useful UV absorbers include CYASORB UV 5411, TINUVIN 130 andTINUVIN 328 commercially available Ciba Specialty Chemicals, andSANDOVAR 3206 commercially available from Clariant Corp. of Charlotte,N.C. Examples of useful hindered amine light stabilizers includeSANDOVAR 3056 commercially available from Clariant Corp. of Charlotte,N.C. Examples of useful surfactants include BYK 306 commerciallyavailable from BYK Chemie of Wesel, Germany.

Such additives can be present in an amount such that the additiveconstitutes less than about 30 percent by weight, or less than about 15percent by weight, or less than about 5 percent by weight, or less thanabout 3 percent by weight, based on the total weight of the polymer. Insome non-limiting embodiments, the aforementioned optional additives canbe pre-mixed with the polyisocyanate(s) or isocyanate functionalprepolymer. In other non-limiting embodiments, the optional additivescan be pre-mixed with the polyol(s) or urethane prepolymer.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethanes of Group A comprising the step of reacting ina one pot process components comprising: about 1 equivalent of at leastone polyisocyanate; about 0.1 to about 0.9 equivalents of at least onebranched polyol having 4 to 18 carbon atoms and at least 3 hydroxylgroups; and about 0.1 to about 0.9 equivalents of at least one diolhaving 2 to 18 carbon atoms, wherein the components are essentially freeof polyester polyol and polyether polyol.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethanes of Group A comprising the steps of:reacting at least one polyisocyanate and at least one branched polyolhaving 4 to 18 carbon atoms and at least 3 hydroxyl groups to form apolyurethane prepolymer; and reacting the polyurethane prepolymer withat least one diol having 2 to 18 carbon atoms to form the polyurethane.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethanes of Group B comprising the steps of:

(a) reacting (i) about 1 equivalent of at least one polyisocyanate; and(ii) about 0.1 to about 0.5 equivalents of at least one diol having 2 to18 carbon atoms to form an isocyanate functional urethane prepolymer;

(b) reacting the isocyanate functional urethane prepolymer with about0.05 to about 0.9 equivalents of at least one branched polyol having 4to 18 carbon atoms and at least 3 hydroxyl groups and up to about 0.45equivalents of at least one diol having 2 to 18 carbon atoms, whereinthe reaction product components are essentially free of polyester polyoland polyether polyol.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethanes of Group C comprising the step of reacting ina one pot process components comprising: at least one polyisocyanatetrimer or branched polyisocyanate, the polyisocyanate having at leastthree isocyanate functional groups; and at least one aliphatic polyolhaving 4 to 18 carbon atoms and at least two hydroxyl groups, whereinthe reaction product components are essentially free of polyester polyoland polyether polyol.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethanes of Group D comprising the step of reacting ina one pot process components comprising: at least one polyisocyanate; atleast one branched polyol having 4 to 18 carbon atoms and at least 3hydroxyl groups; and at least one polyol having one or more bromineatoms, one or more phosphorus atoms or combinations thereof.

In other non-limiting embodiments, the present invention provides methodof preparing polyurethanes of Group D comprising the steps of: reactingat least one polyisocyanate and at least one branched polyol having 4 to18 carbon atoms and at least 3 hydroxyl groups to form a polyurethaneprepolymer; and reacting the polyurethane prepolymer with at least onepolyol having one or more bromine atoms, one or more phosphorus atoms orcombinations thereof to form the polyurethane. In some non-limitingembodiments, about 0.1 to about 0.15 equivalents of the branched polyolare reacted with about 1 equivalent of polyisocyanate in step (a) andstep (b) further comprises reacting the polyurethane prepolymer with thepolyol and about 0.15 to about 0.9 equivalents of the branched polyol toform the polyurethane.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethanes of Group E comprising the step of reacting ina one pot process components comprising: about 1 equivalent of at leastone polyisocyanate; about 0.3 to about 1 equivalents of at least onebranched polyol having 4 to 18 carbon atoms and at least 3 hydroxylgroups; and about 0.01 to about 0.3 equivalents of at least onepolycarbonate diol, wherein the reaction product components areessentially free of polyether polyol and amine curing agent.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethanes of Group E comprising the steps of:reacting at least one polyisocyanate and at least one branched polyolhaving 4 to 18 carbon atoms and at least 3 hydroxyl groups to form apolyurethane prepolymer; and reacting the polyurethane prepolymer withat least one polycarbonate diol to form the polyurethane.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethanes of Group F comprising the step of reacting ina one pot process components comprising: (a) about 1 equivalent of atleast one polyisocyanate; (b) about 0.3 to about 1 equivalents of atleast one branched polyol having 4 to 18 carbon atoms and at least 3hydroxyl groups; (c) about 0.01 to about 0.3 equivalents of at least onepolycarbonate diol; and (d) about 0.1 to about 0.9 equivalents of atleast one diol having 2 to 18 carbon atoms, wherein the reaction productcomponents are essentially free of polyether polyol.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethanes of Group F comprising the stepsof:(a) reacting at least one polyisocyanate and at least one branchedpolyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups toform a polyurethane prepolymer; and (b) reacting the polyurethaneprepolymer with at least one polycarbonate diol and at least one diolhaving 2 to 18 carbon atoms to form the polyurethane, wherein thereaction product components are essentially free of polyether polyol.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethanes of Group G comprising the step of reacting ina one pot process components comprising: about 1 equivalent of at leastone polyisocyanate; about 0.3 to about 1 equivalents of at least onebranched polyol having 4 to 18 carbon atoms and at least 3 hydroxylgroups; and about 0.01 to about 0.3 equivalents of at least one polyolselected from the group consisting of polyester polyol, polycaprolactonepolyol and mixtures thereof; and about 0.1 to about 0.7 equivalents ofat least one aliphatic diol, wherein the reaction product components areessentially free of polyether polyol and amine curing agent.

In other non-limiting embodiments, the present invention providesmethods of preparing polyurethanes of Group G comprising the steps of:reacting at least one polyisocyanate and at least one branched polyolhaving 4 to 18 carbon atoms and at least 3 hydroxyl groups to form apolyurethane prepolymer; and reacting the polyurethane prepolymer withat least one polyol selected from the group consisting of polyesterpolyol, polycaprolactone polyol and mixtures thereof and about 0.1 toabout 0.7 equivalents of at least one aliphatic diol to form thepolyurethane.

In some non-limiting embodiments, the present invention provides methodsof preparing polyurethanes of Group H comprising the steps of: reactingcomponents comprising: at least one polyisocyanate; at least onepolycaprolactone polyol; and at least one polyol selected from the groupconsisting of polyalkylene polyol, polyether polyol and mixturesthereof, to form a polyurethane prepolymer; and reacting the prepolymerwith at least one diol having 2 to 18 carbon atoms to form thepolyurethane.

Polv(ureaurethanes)

Poly(ureaurethane)s can be prepared from any of the above polyurethanesof Groups A-H by including one or more amine curing agents in thereaction components. The amine functionality of the amine curing agentcan react with isocyanate groups to form urea linkages or units withinthe polyurethane matrix. Suitable amounts of amine curing agents andreaction conditions are discussed in detail above.

Poly(ureaurethane) Synthesis A

Alternatively or additionally, urea linkages or units can be formedwithin the polyurethane matrix to the extent desired by reactingisocyanate functional groups of the polyisocyanate with water. As shownin Step 1 of the reaction scheme of Poly(ureaurethane) Synthesis Abelow, isocyanate functional groups are converted to carbamatefunctional groups by the reaction with water. In some non-limitingembodiments, the equivalent ratio of NCO:water ranges from about 10:1 toabout 2:1, or about 5:1 to about 2:1, or about 3:1 to about 2:1.

The isocyanate shown in Step 1 is a diisocyanate in which R is anylinking group, such as aliphatic, cycloaliphatic, aromatic, heterocycle,etc. as described in detail above. However, one skilled in the art wouldunderstand that the isocyanate can have one or more, two or more, threeor more or a higher number of isocyanate functional groups, as desired.Examples of suitable isocyanates can be any of the isocyanates discussedabove. In some non-limiting embodiments, the polyisocyanate is one ormore aliphatic polyisocyanates. In some non-limiting embodiments, thepolyisocyanate is 4,4′-methylene-bis-(cyclohexyl isocyanate) (such asDESMODUR W).

Removal of carbon dioxide facilitates conversion of the carbamate groupsinto amine groups. Excess isocyanate is desirable to ensure essentiallycomplete consumption of the water. Also, it is desirable to removeessentially all of the carbon dioxide generated to facilitate conversionto amine groups. The water can be reacted with the polyisocyanate orpolyurethane polyisocyanate prepolymer at a temperature of up to about60° C. under vacuum. The vacuum pressure should be low enough so as notto remove water from the system, and can range for example from about 10to about 20 mm Hg (about 1333 to about 2666 Pa) for a time period ofabout 10 to about 30 minutes. After the reaction is essentiallycomplete, i.e., no further carbon dioxide is formed, the temperature canbe increased to at least about 100° C. or about 110° C. and heated forabout 2 to about 24 hours, or about 2 hours, using 10 ppm or more ofcatalyst such as dibutyltin diacetate. After substantially all of thewater reacts with the excess isocyanate, the amine that is formed reactsessentially instantaneously with the isocyanate.

As is well known to those skilled in the art, certain amine curingagents (such as aliphatic amine curing agents having 2 to 18 carbonatoms, e.g., ethylene diamine, diethylenediamine, diaminobutane, PACM,diamine hexane, 1,10-decanediamine) are highly reactive and impracticalto use under normal production conditions because the aminefunctionality begins to react with oxygen present in the ambient airvery quickly to discolor the polymerizate. Aliphatic amine curing agentsare typically very hygroscopic and difficult to keep dry. Generally,aliphatic amines are so reactive as to be impractical for making 100%solids, transparent, low color and low haze plastics.

By forming the amine in situ as discussed above and shown in Step 2,amines can be generated in situ that normally are not practical to useunder normal production conditions without formation of undesirable sideproducts, color or haze. Also, the rate of reaction can be more easilyregulated. This reaction can be used for any type of polyisocyanatedescribed above, but is especially useful for converting aliphaticpolyisocyanates to amines as described above.

As shown in Step 2 above, the amine formed in situ reacts with anotherisocyanate to form a urea group. Use of excess polyisocyanate permitsformation of an isocyanate functional urea prepolymer. In somenon-limiting embodiments, the equivalent ratio of NCO:amine functionalgroups ranges from about 1:0.05 to about 1:0.7, or about 1:0.05 to about1:0.5, or about 1:0.05 to about 1:0.3. Suitable reaction temperaturescan range from about 25° C. to about 60° C. with a catalyst such as atin catalyst. After the water is reacted and the carbon dioxide removed,the reaction temperature can be increased up to about 90° C. for about 2to about 4 hours. Alternatively, the reaction can proceed at about 25°C. for up to about 8 hours until complete. Optionally, one or morepolyols or diols as described above can be included in this reaction toform isocyanate functional urethane prepolymers, as shown inPoly(ureaurethane) Synthesis B, described in further detail below.

As shown in Step 3 of the reaction scheme of Poly(ureaurethane)Synthesis A above, the polyol and/or diol can be reacted with theisocyanate functional urea prepolymer(s) to form poly(ureaurethane)s ofthe present invention. The polyol shown in Step 3 can be a diol (m=2),triol (m=3) or higher hydroxyl functional material (m=4 or more) asdescribed above in which R is any linking group, such as aliphatic,cycloaliphatic, aromatic, heterocycle, etc. as described in detail abovewith respect to the polyols. Examples of suitable polyols can be any ofthe polyos discussed above. In some non-limiting embodiments, the polyolcan be trimethylolpropane and butanediol and/or pentanediol. Suitableamounts of polyols for reacting with the isocyanate functional ureaprepolymer as polyisocyanate are discussed in detail above. In the abovepoly(ureaurethane), x can range from 1 to about 100, or about 1 to about20.

In some non-limiting embodiments, to form the poly(ureaurethane) theisocyanate functional prepolymer is heated to a temperature of about 90°C., the polyol(s) are added and heated to about 90° C. The temperaturecan be increased to about 100° C. or about 11° C. to facilitatecompatibilization, then about 2 to about 4 mm of vacuum can be appliedfor about 3 to about 5 minutes.

To prepare an article, for example, the mixture can be poured orpressure cast into a release-coated glass casting mold to form anarticle of desired thickness and dimensions. In some embodiments, thecasting mold is preheated to a temperature of about 200° F. (93.3° C.).The filled mold or cell can be placed in an oven at a temperature ofabout 250° F. (121° C.) to about 320° F. (160° C.) and cured for about24 to about 48 hours, for example. The cell can be removed from the ovenand cooled to a temperature of about 25° C. and the cured polymerreleased from the casting mold.

Group I

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s of Group I comprising a reaction product ofcomponents comprising: (a) at least one isocyanate functional ureaprepolymer comprising a reaction product of: (1) at least onepolyisocyanate; and (2) water; and (b) at least one branched polyolhaving 4 to 18 carbon atoms and at least 3 hydroxyl groups, wherein thereaction product components are essentially free or free of amine curingagents. Suitable polyisocyanates and branched polyol(s) having 4 to 18carbon atoms are described in detail above. If present, the amine curingagent(s) can be present in an amount as defined above as essentiallyfree. Any of the other optional polyols, catalysts or other additivesdescribed above can be included as reaction components in amounts asdescribed above with respect to the foregoing Groups A-H.

In some non-limiting embodiments, the present invention provides methodsof preparing poly(ureaurethane)s of Group I comprising the steps of: (a)reacting at least one polyisocyanate and water to form an isocyanatefunctional urea prepolymer; and (b) reacting reaction product componentscomprising the isocyanate functional urea prepolymer with at least onebranched polyol having 4 to 18 carbon atoms and at least 3 hydroxylgroups, wherein the reaction product components are essentially free ofamine curing agent. The reaction synthesis can be as described abovewith respect to Poly(ureaurethane) Synthesis A. Optionally, a portion ofone or more polyols or diols as described above can be included in thisreaction to form isocyanate functional urethane prepolymer which is thenfurther reacted with another portion of polyol and/or diol, as shown inPoly(ureaurethane) Synthesis B, described in further detail below.

Group J

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s of Group J comprising a reaction product ofcomponents comprising: (a) at least one isocyanate functional ureaprepolymer comprising a reaction product of: (1) at least onepolyisocyanate selected from the group consisting of polyisocyanatetrimers and branched polyisocyanates, the polyisocyanate having at leastthree isocyanate functional groups; and (2) water; and (b) at least onealiphatic polyol having 4 to 18 carbon atoms and at least 2 hydroxylgroups.

Examples of suitable polyisocyanate trimers and branched polyisocyanatesand polyol(s) are discussed above. Any of the other optional polyols,amine curing agent, catalysts or other additives described above can beincluded as reaction components in amounts as described above withrespect to the foregoing Groups A-H. In some non-limiting embodiments,the reaction components are essentially free or free of amine curingagents as described above.

In other non-limhiting embodiments, the present invention providesmethods of preparing poly(ureaurethane) comprising the steps of: (a)reacting at least one polyisocyanate selected from the group consistingof polyisocyanate trimers and branched polyisocyanates and water to forman isocyanate functional urea prepolymer; and (b) reacting reactionproduct components comprising the isocyanate functional urea prepolymerwith at least one aliphatic polyol having 4 to 18 carbon atoms and atleast 2 hydroxyl groups, wherein the reaction product components areessentially free of amine curing agent.

The reaction synthesis can be as described above with respect toPoly(ureaurethane) Synthesis A. Optionally, a portion of one or morepolyols or diols as described above can be included in this reaction toform isocyanate functional urethane prepolymer which is then furtherreacted with another portion of polyol and/or diol, as shown inPoly(ureaurethane) Synthesis B, described in further detail below.

Poly(ureaurethane) Synthesis B

As shown generally in Poly(ureaurethane) Synthesis B below, in othernon-limiting embodiments urea linkages or units can be formed within thepolyurethane matrix to the extent desired by reacting polyisocyanate(s)and a portion of the polyol(s) to form at least one isocyanatefunctional urethane prepolymer, and then reacting the isocyanatefunctional urethane prepolymer(s) with water. As shown in Step 1 of thereaction scheme of Poly(ureaurethane) Synthesis B below, a portion ofthe polyol(s) and/or diol(s) can be reacted with polyisocyanate(s) toform the at least one isocyanate functional urethane prepolymer. In somenon-limiting embodiments, the equivalent ratio of NCO:OH functionalgroups ranges from about 1:0.05 to about 1:0.7, or about 1:0.05 to about1:0.5, or about 1:0.05 to about 1:0.3. It is desirable to use excessisocyanate to ensure essentially complete conversion of the hydroxylgroups to urethane groups.

The isocyanate shown in Step 1 is a diisocyanate in which R is anylinking group, such as aliphatic, cycloaliphatic, aromatic, heterocycle,etc. as described in detail above. However, one skilled in the art wouldunderstand that the isocyanate can have one or more, two or more, threeor more or a higher number of isocyanate functional groups, as desired.Examples of suitable isocyanates can be any of the polyisocyanatesdiscussed above. In some non-limiting embodiments, the polyisocyanate isone or more aliphatic polyisocyanates. In some non-limiting embodiments,the polyisocyanate is 4,4′-methylene-bis-(cyclohexyl isocyanate) (suchas DESMODUR W).

The polyol shown in Step 1 can be a diol (m=2), triol (m=3) or higherhydroxyl functional material (m=4 or more) as described above in which Ris any linking group, such as aliphatic, cycloaliphatic, aromatic,heterocycle, etc. as described in detail above with respect to thepolyols. Examples of suitable polyols can be any of the polyolsdiscussed above. In some non-limiting embodiments, the polyol can betrimethylolpropane and butanediol and/or pentanediol. Optionally, one ormore catalysts such as are described above can be used to facilitate thereaction. The polyisocyanate can be reacted with the polyol to form theisocyanate functional urethane prepolymer by charging the reactants intoa kettle and adding about 10 ppm or more of catalyst, such as a tin,bismuth or zirconium catalyst. The mixture can be heated to atemperature of about 100° C. or about 110° C. for about 2 to about 4hours until all of the hydroxyl functionality is reacted. FTIRspectroscopy can be used to determine the extent of reaction.

Urea linkages or units can be formed within the polyurethane matrix tothe extent desired by reacting isocyanate functional groups of theisocyanate functional urethane prepolymer with water. As shown in Step 2of the reaction scheme of Poly(ureaurethane) Synthesis B below,isocyanate functional groups are converted to carbamate functionalgroups by the reaction with water. In some non-limiting embodiments, theequivalent ratio of NCO: water ranges from about 1:0.05 to about 1:0.7,or about 1:0.05 to about 1:0.5, or about 1:0.05 to about 1:0.3.

Removal of carbon dioxide facilitates conversion of the carbamate groupsinto amine groups. Excess isocyanate is desirable to ensure essentiallycomplete consumption of the water. Also, it is desirable to removeessentially all of the carbon dioxide generated to facilitate conversionto amine groups. To prevent the removal of water under vacuum, thereaction can be started at a temperature of about 25° C., then raised toa temperature of about 60° C. while applying vacuum to remove the carbondioxide. After cessation of carbon dioxide formation, the reactiontemperature can be increased to about 100° C. or about 11° C. for about2 to about 4 hours.

As discussed above, certain amine curing agents (such as aliphatic aminecuring agents) are highly reactive and impractical to use under normalproduction conditions. By forming the amine in situ as discussed aboveand shown in Step 2, amines can be generated in situ that normally arenot practical to use under normal production conditions withoutformation of undesirable side products. Also, the rate of reaction canbe more easily regulated. This reaction can be used for any type ofpolyisocyanate described above, but is especially useful for convertingaliphatic polyisocyanates to amines as described above.

As shown in Step 3 below, the amine formed in situ reacts with anotherisocyanate to form a urea group. Use of excess polyisocyanate permitsformation of an isocyanate functional ureaurethane prepolymer. Theisocyanate functional ureaurethane prepolymer can be prepared byreacting a stoichiometric excess of the polyisocyanate with the amineunder substantially anhydrous conditions at a temperature ranging fromabout 25° C. and about 150° C. or about 110° C. until the reactionbetween the isocyanate groups and the amine groups is substantiallycomplete. The polyisocyanate and amine components are suitably reactedin such proportions that the ratio of number of isocyanate groups to thenumber of amine groups is in the range of about 1:0.05 to about 1:0.7,or within the range of about 1:0.05 to 1:0.3.

As shown in Step 4 of the reaction scheme of Poly(ureaurethane)Synthesis B below, the isocyanate functional ureaurethane prepolymer canbe reacted with another portion of polyol and/or diol to form thepoly(ureaurethane)s of the present invention. The polyol shown in Step 4can be a diol, triol or higher hydroxyl functional material as describedabove in which R is any linking group, such as aliphatic,cycloaliphatic, aromatic, heterocycle, etc. as described in detail abovewith respect to the polyols. Examples of suitable polyols can be any ofthe polyols discussed above. In some non-limiting embodiments, thepolyol can be trimethylolpropane and butanediol and/or pentanediol.Suitable amounts of polyols for reacting with the isocyanate functionalureaurethane prepolymer as polyisocyanate are discussed in detail above.

The isocyanate functional ureaurethane prepolymer can be reacted withthe other portion of polyol and/or diol (n=2 or more) undersubstantially anhydrous conditions at a temperature ranging from about120° C. to about 160° C. until the reaction between the isocyanategroups and the hydroxyl groups is substantially complete. The isocyanatefunctional ureaurethane prepolymer and polyol(s) and/or diol(s)components are suitably reacted in such proportions that the ratio ofnumber of isocyanate groups to the number of hydroxyl groups is in therange of about 1.05:1 to about 1:1 In the poly(ureaurethane) of Group K,y can range from 1 to about 500 or higher, or about 1 to about 200.

The cure temperature depends upon the glass transition temperature ofthe final polymer. In some embodiments, for complete cure the curetemperature should be greater than the glass transition temperature. Forexample, the cure temperature can range from about 140° C. to about 180°C. or about 143° C. to about 180° C.

Group K

In some non-limiting embodiments, the present invention providespoly(ureaurethane)s of Group K comprising a reaction product ofcomponents comprising: (a) at least one isocyanate functionalureaurethane prepolymer comprising the reaction product of: (1) at leastone isocyanate functional urethane prepolymer comprising the reactionproduct of: (i) a first amount of at least one polyisocyanate; and (ii)a first amount of at least one branched polyol; and (2) water, to forman isocyanate functional ureaurethane prepolymer; and (b) a secondamount of at least one polyisocyanate and a second amount of at leastone branched polyol.

Examples of suitable polyisocyanates and polyol(s) are discussed above.Any of the other optional polyols, amine curing agents, catalysts orother additives described above can be included as reaction componentsin amounts as described above with respect to the foregoing Groups A-G.In some non-limiting embodiments, the reaction components areessentially free or free of amine curing agent as described above orfree of amine curing agent.

In other non-limiting embodiments, the present invention providesmethods of preparing poly(ureaurethane)s of Group K comprising the stepsof: (a) reacting at least one polyisocyanate and at least one branchedpolyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups toform an isocyanate functional urethane prepolymer; (b) reacting theisocyanate functional urethane prepolymer with water and polyisocyanateto form an isocyanate functional ureaurethane prepolymer; and (c)reacting reaction product components comprising the isocyanatefunctional ureaurethane prepolymer with at least one aliphatic polyolhaving 4 to 18 carbon atoms and at least 2 hydroxyl groups, wherein thereaction product components are essentially free of amine curing agent.The reaction synthesis can be as described above with respect toPoly(ureaurethane) Synthesis B.

Group L

In other non-limiting embodiments, the present invention providespoly(ureaurethane)s of Group L comprising a reaction product ofcomponents comprising: (a) at least one isocyanate functionalureaurethane prepolymer comprising the reaction product of: (a) (1) atleast one isocyanate functional urethane prepolymer comprising thereaction product of: (i) a first amount of at least one polyisocyanateselected from the group consisting of polyisocyanate trimers andbranched polyisocyanates, the polyisocyanate having at least threeisocyanate functional groups; and (ii) a first amount of at least onealiphatic polyol; and (2) water, to form an isocyanate functionalureaurethane prepolymer; and (b) a second amount of at least onepolyisocyanate and a second amount of at least one aliphatic polyol.

Examples of suitable polyisocyanate trimers and branched polyisocyanateshaving at least three isocyanate functional groups and polyol(s) arediscussed above. Any of the other optional polyols, amine curing agent,catalysts or other additives described above can be included as reactioncomponents in amounts as described above with respect to the foregoingGroups A-G. In some non-limiting embodiments, the reaction componentsare essentially free or free of amine curing agent as described above.

In other non-limiting embodiments, the present invention providesmethods of preparing poly(ureaurethane)s of Group L comprising the stepsof: (a) reacting at least one polyisocyanate selected from the groupconsisting of polyisocyanate trimers and branched polyisocyanates and atleast one aliphatic polyol having 4 to 18 carbon atoms and at least 2hydroxyl groups to form an isocyanate functional urethane prepolymer;(b) reacting the isocyanate functional urethane prepolymer with waterand polyisocyanate to form an isocyanate functional ureaurethaneprepolymer; and (c) reacting reaction product components comprising theisocyanate functional ureaurethane prepolymer with at least onealiphatic polyol having 4 to 18 carbon atoms and at least 2 hydroxylgroups, wherein the reaction product components are essentially free orfree of amine curing agent. The reaction synthesis can be as describedabove with respect to Poly(ureaurethane) Synthesis B.

As discussed above, poly(ureaurethane)s can be prepared by including oneor more amine curing agents in the reaction components. The aminefunctionality of the amine curing agent can react with isocyanate groupsto form urea linkages or units within the polyurethane matrix.

Group M

In other non-limiting embodiments, the present invention providespoly(ureaurethane)s of Group M comprising a reaction product ofcomponents comprising: about 1 equivalent of at least onepolyisocyanate; about 0.1 to about 0.9 equivalents of at least onebranched polyol having 4 to 18 carbon atoms and at least 3 hydroxylgroups; about 0.1 to about 0.9 equivalents of at least one aliphaticdiol having 2 to 18 carbon atoms; and at least one amine curing agent,wherein the reaction product components are essentially free or free ofpolyester polyol and polyether polyol.

Non-limiting examples of suitable polyisocyanates, branched polyolshaving 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphaticdiols and amine curing agents for use as reaction components forpreparing the polyurethanes of Group M are discussed in detail abovewith respect to Group A.

In some non-limiting embodiments, the amount of branched polyol used toform the polyurethane of Group M can be about 0.3 to about 0.98equivalents, in other non-limiting embodiments about 0.5 to about 0.98equivalents, and in other non-limiting embodiments about 0.3 equivalentsor about 0.9 or about 0.98 equivalents.

In some non-limiting embodiments, the amount of aliphatic diols used toform the polyurethane of Group M can be about 0.1 to about 0.7equivalents, in other non-limiting embodiments about 0.1 to about 0.5equivalents, and in other non-limiting embodiments about 0.3equivalents.

In some non-limiting embodiments, the amount of amine curing agent usedto form the polyurethane of Group M can be about 0.1 to about 0.9equivalents, in other non-limiting embodiments about 0.1 to about 0.7equivalents, and in other non-limiting embodiments about 0.3equivalents.

With respect to poly(ureaurethane)s of Group M, essentially free ofpolyester polyol and polyether polyol means that the polyester polyoland polyether polyol can be present as reaction components in respectiveamounts as described for the polyurethane of Group A above, or thereaction components can be free of one or both of polyester polyol andpolyether polyol.

Any of the other optional polyols, catalysts or other additivesdescribed above can be included as reaction components in amounts asdescribed above with respect to the foregoing Groups A-H.

In other non-limiting embodiments, the present invention providesmethods of preparing poly(ureaurethane) comprising the step of reactingin a one pot process components comprising: at least one polyisocyanate;at least one branched polyol having 4 to 18 carbon atoms and at least 3hydroxyl groups; at least one aliphatic diol having 2 to 18 carbonatoms; and amine curing agent, wherein the reaction product componentsare essentially free or free of polyester polyol and polyether polyol.

Group N

In other non-limiting embodiments, the present invention providespoly(ureaurethane)s of Group N comprising a reaction product ofcomponents comprising: (a) at least one polyisocyanate selected from thegroup consisting of polyisocyanate trimers and branched polyisocyanates,the polyisocyanate having at least three isocyanate functional groups;(b) about 0.1 to about 0.9 equivalents of at least one polyol having 4to 18 carbon atoms and at least 2 hydroxyl groups; and (c) at least oneamine curing agent, wherein the reaction product components areessentially free or free of polyester polyol and polyether polyol.

Non-limiting examples of suitable polyisocyanates, branched polyolshaving 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphaticdiols and amine curing agents for use as reaction components forpreparing the polyurethanes of Group N are discussed in detail abovewith respect to Groups A-C.

In some non-limiting embodiments, the amount of branched polyol used toform the polyurethane of Group N can be about 0.3 to about 0.98equivalents, in other non-limiting embodiments about 0.5 to about 0.98equivalents, and in other non-limiting embodiments about 0.3 equivalentsor about 0.9 or about 0.98 equivalents.

In some non-limiting embodiments, the amount of aliphatic diols used toform the polyurethane of Group N can be about 0.1 to about 0.7equivalents, in other non-limiting embodiments about 0.1 to about 0.5equivalents, and in other non-limiting embodiments about 0.3equivalents.

In some non-limiting embodiments, the amount of amine curing agent usedto form the polyurethane of Group N can be about 0.1 to about 0.7equivalents, in other non-limiting embodiments about 0.1 to about 0.5equivalents, and in other non-limiting embodiments about 0.3equivalents.

With respect to poly(ureaurethane)s of Group N, essentially free ofpolyester polyol and polyether polyol means that the polyester polyoland polyether polyol can be present as reaction components in respectiveamounts as described for the polyurethane of Group A above, or thereaction components can be free of one or both of polyester polyol andpolyether polyol.

Any of the other optional polyols, catalysts or other additivesdescribed above can be included as reaction components in amounts asdescribed above with respect to the foregoing Groups A-H.

In other non-limiting embodiments, the present invention providesmethods of preparing poly(ureaurethane) comprising the step of reactingin a one pot process components comprising: at least one polyisocyanateselected from the group consisting of polyisocyanate trimers andbranched polyisocyanates; at least one aliphatic polyol having 4 to 18carbon atoms and at least 3 hydroxyl groups; at least one aliphatic diolhaving 2 to 18 carbon atoms; and amine curing agent, wherein thereaction product components are essentially free or free of polyesterpolyol and polyether polyol.

In some embodiments, the poly(ureaurethanes) of Groups I-N of thepresent invention can be thermosetting.

Group O

In some non-limiting embodiments, the present invention providespolyurethane materials comprising a first portion of crystallineparticles having self-orientation and bonded together to fix theirorientation along a first crystallographic direction and a secondportion of crystalline particles having self-orientation and bondedtogether to fix their orientation along a second crystallographicdirection, the first crystallographic direction being different from thesecond crystallographic direction, wherein said crystalline particlescomprise at least about 30% of the total volume of the polyurethanematerial.

The particles interact with one another or with a substrate surface toalign their crystallographic axes in one, two or three dimensions. Asused herein, “align” or “aligned” with respect to the crystallineparticles means that the particles of that crystalline portion arearranged in an array of generally fixed position and orientation. Thepreferred degree of alignment will depend on the intended applicationfor the material. For purposes of alignment, it is desirable that theparticles have uniform shapes with dominant planar surfaces in asuitable orientation, such as perpendicular to or parallel to, withrespect to the desired direction of alignment.

In some non-limiting embodiments, the first portion of the crystallineparticles is aligned in two dimensions. In some non-limitingembodiments, the first portion of the crystalline particles is alignedin three dimensions. In some embodiments, the crystalline particles arealigned along a distance ranging from about 1 nm to about 50 nm alongany direction.

In some non-limiting embodiments, the second portion of the crystallineparticles is aligned in two dimensions. In some non-limitingembodiments, the second portion of the crystalline particles is alignedin three dimensions.

The crystalline particles of the present invention have at least“Self-Aligning” morphologies. As used herein, “Self-Aligning”morphologies include any particles that are capable of self-organizingto form a polycrystalline structure wherein the single particles arealigned along at least one crystallographic direction into areas ofhigher density and order, for example like lamellae. Examples of crystalparticle morphologies with Self-Aligning morphologies include cubicparticles, hexagonal platelets, hexagonal fibers, rectangular platelets,rectangular particles, triangular platelets, square platelets,tetrahedral, cube, octahedron and mixtures thereof.

Self-Aligning morphologies may establish an orientation that could be upto about 10 degrees from the desired alignment direction, yet stillsufficiently capture the desired properties. Thus, particles having suchmorphologies include particles that essentially have the desiredmorphology. For instance, for particles that are cubes, the particlesneed not be perfect cubes. The axes need not be at perfect 90 degreeangles, nor exactly equal in length. Corners may also be cut off of theparticles. Furthermore, “cube” or “cubic” is intended to refer tomorphology, and is not intended to limit the particles to cubic crystalsystems. Instead, single crystal particles that have orthorhombic,tetragonal or rhombohedral crystal structure may also be employed ascubes if they possess the defined cubic morphology. In other words, anyessentially orthogonal single crystal particles in which the faces areessentially square, essentially rectangular, or both, that possess anessentially cubic morphology are considered cubes for purposes of thepresent invention.

The crystalline particles can be aligned in monolithic structuresconsisting of a single layer of crystals or multiple layers of crystals.The layer or layers are generally planar, although the layers canconform to curved surfaces or complex geometries depending on the shapeof the supporting substrate material during formation and curing of thepolyurethane.

The polycrystalline materials of the present invention are prepared bypacking and aligning a plurality of single crystal particles into analigned array to achieve one, two and three-dimensional alignment. Insome non-limiting embodiments, the particles can self-assemble intoarrays upon aging or heat treatment. In some non-limiting embodiments,to obtain a level of solid state diffusion sufficient to bind togetheradjacent particles, a temperature above about half of the meltingtemperature is required, which is most generally in the range of about35° C. to about 100° C. The temperature range selected will depend uponthe material being bonded, but can be readily determined by those ofordinary skill in the art without undue experimentation within thedefined range. The preparation steps may be repeated to form apolycrystalline material having multiple layers of aligned particles.The resulting material is essentially a three-dimensional object withone, two, or three dimensional alignment of single crystal particleswithin.

FIG. 4 is a TEM photomicrograph showing a casting prepared from apolyurethane according to Example A, Formulation 2. This casting wasanalyzed, using TEM, two weeks after polymerization of the polyurethane.The casting had been stored at ambient temperature (about 25° C.) forthe two week period. As shown in FIG. 4, no discernible regions ofaligned crystals were observed.

FIG. 5 is a TEM photomicrograph showing a casting of a polyurethaneaccording to Example A, Formulation 2. This casting was analyzed, usingTEM, three weeks after polymerization of the polyurethane. The castinghad been stored at ambient temperature (about 25° C.) for the three weekperiod. As shown in FIG. 5, initial formation of crystalline domains isobserved.

FIG. 6 is a TEM photomicrograph showing a casting of a polyurethaneaccording to Example A, Formulation 2. This casting was analyzed, usingTEM, seven months after polymerization of the polyurethane. The castinghad been stored at ambient temperature (about 25° C.) for the sevenmonth period. In the photomicrograph FIG. 6, a region of alignedcrystals generally parallel to the arrows is shown.

FIG. 7 is an electron diffraction pattern of the polyurethane Example A,Formulation 2 stored at ambient temperature (about 25° C.) for sevenmonths. The bright spots in the pattern are reflections from thecrystalline lattice planes, which are about 8 nanometers by about 4nanometers in size.

FIG. 8 is a TEM photomicrograph showing a casting of a polyurethaneaccording to Example A, Formulation 2 prepared after aging at ambienttemperature for about 7 months. In this photomicrograph FIG. 8, manyregions or domains of aligned crystals generally parallel to the arrowsare shown, the domains being oriented in different directions andshowing a higher density of domains than the samples aged for threeweeks.

FIG. 9 is a TEM photomicrograph showing a first portion of a casting ofa polyurethane according to Example A, Formulation 2 prepared afteraging at ambient temperature for about two to four weeks. The castinghad been stored at ambient temperature for the two to four week period.As shown in FIG. 9, no discernible regions of aligned crystals wereobserved.

FIG. 10 is a TEM photomicrograph showing a second portion of the castingof the polyurethane according to Example A, Formulation 2 shown in FIG.9. As shown in the circled area in FIG. 10, initial formation ofcrystalline domains is observed.

The sample shown in FIGS. 9 and 10 had a Gardner Impact Strength of 180in-lbs.

FIG. 11 is a TEM photomicrograph showing a casting of a polyurethaneaccording to Example A, Formulation 2. This casting was analyzed, usingTEM, about two to about four weeks after polymerization of thepolyurethane. The casting had been stored at ambient temperature for thetwo to four week period. In the photomicrograph FIG. 11, regions ofaligned crystals in the circled areas are shown.

FIG. 12 is a TEM photomicrograph showing a first portion of a casting ofa polyurethane according to Example A, Formulation 2 prepared afteraging at ambient temperature for about 7 months. In this photomicrographFIG. 12, a large region or domain of aligned crystals is shown.

FIG. 13 is a TEM photomicrograph showing a second portion of a castingof a polyurethane according to Example A, Formulation 2 shown in FIG.12. In this photomicrograph FIG. 13, many regions or domains of alignedcrystals are shown, the domains being oriented in different directionsand showing a higher density of domains than the samples aged for ashorter period of time.

The sample shown in FIGS. 12 and 13 had a Gardner Impact Strength of 640in-lbs.

FIG. 14 is a graph of heat flow as a function of temperature measuredusing Differential Scanning Calorimetry (DSC) for castings of apolyurethane according to Example A, Formulation 2 measured after agingat ambient conditions for two weeks, three months and seven months,respectively. The melting endotherm enthalpy of the crystalline domainsincreases with time, showing a change in polymer morphology andmicrostructure with time, even though the polymer is glassy and highlycrosslinked with a glass transition temperature of 235° F. (113° C.). Asthe number and size of the crystalline domains increases, the meltingenthalpy increases. The Gardner Impact Strength increased over time. Attwo weeks, the Gardner Impact Strength was 180 in-lbs. At three months,the Gardner Impact Strength was 380 in-lbs. At seven months, the GardnerImpact Strength was 640 in-lbs.

FIG. 15 is a graph of Gardner Impact as a function of Young's Modulusfor castings of a polyurethane according to Example A, Formulations 2and 1, respectively, measured after aging at ambient conditions forseven months and one year, respectively. At.seven months for Formulation2, the Gardner Impact Strength was 640 in-lbs. At one year forFormulation 1, the Gardner Impact Strength was 400 in-lbs.

In some non-limiting embodiments, the polyurethane material comprises amonolithic agglomerate of the first portion of the crystalline particleswith low-angle grain boundaries therebetween bonded together by apolymer phase.

In some non-limiting embodiments, the polyurethane material comprises amonolithic agglomerate of the second portion of the crystallineparticles with low-angle grain boundaries therebetween bonded togetherby a polymer phase.

In some non-limiting embodiments, the polyurethane material comprises amonolithic agglomerate of the first portion of the crystalline particleswith low-angle grain boundaries and a generally amorphous phasetherebetween.

In some non-limiting embodiments, the polyurethane material comprises amonolithic agglomerate of the second portion of the crystallineparticles with low-angle grain boundaries and a generally amorphousphase therebetween.

In some non-limiting embodiments, the thickness of the first portion ofcrystalline particles is less than about 50 nanometers. In somenon-limiting embodiments, the thickness of the second portion ofcrystalline particles is less than about 50 nanometers. The length andwidth, respectively, of the first portion can vary, for example about 4nm by about 8 nm.

In some non-limiting embodiments, the thickness of the first portion ofcrystalline particles can range from about 10 nanometers to about 100nanometers. In some non-limiting embodiments, the thickness of thesecond portion of crystalline particles can range from about 4nanometers to about 50 nanometers. The length and width, respectively,of the second portion can vary, for example about 4 nm by about 8 nm.

In some non-limiting embodiments, the crystalline particles comprise atleast about 30% of the total volume of the material. In othernon-limiting embodiments, the crystalline particles comprise at leastabout 40%, or at least about 50%, or at least about 60%, or at leastabout 70%, or at least about 80%, or at least about 90% of the totalvolume of the material. The percentage of crystalline particles can bedetermined using DSC. For example, an article prepared from Formulation2 as described below, aged at ambient conditions (about 25° C.) forabout 7 months had a crystallinity of about 43% by volume.

In some non-limiting embodiments, the polyurethane comprises a reactionproduct of components consisting of: (a) about 1 equivalent of4,4′-methylene-bis-(cyclohexyl isocyanate); (b) about 0.3 equivalents oftrimethylolpropane; and (c) about 0.7 equivalents of butanediol orpentanediol. In some non-limiting embodiments, the butanediol is1,4-butanediol. In some non-limiting embodiments, the pentanediol is1,5-pentanediol.

In some non-limiting embodiments, the impact resistance of polyurethanesand poly(ureaurethane)s of Groups A-M above according to the presentinvention can be improved by aging or heat treatment.

In some non-limiting embodiments, the polyurethane material can be agedfor at least about 2 weeks after formation. In some non-limitingembodiments, the polyurethane material can be aged for at least about 2months after formation. In some non-limiting embodiments, thepolyurethane material has been aged for at least about 7 months afterformation.

In some non-limiting embodiments, the polyurethane material has beenheated to a temperature of about 90° C. to about 150° C. or about 200°F. (about 93° C.) to about 290° F. (about 143° C.) for about 1 to about24 hours after formation. In some non-limiting embodiments, thepolyurethane is heated at a temperature sufficient to induce grainboundary mobility, so that the particles grow until impingement ofadjacent crystal grain boundaries prevent further growth. The net resultis a polycrystalline microstructure, the grains of which for allpractical purposes are aligned in two or three dimensions so that itperforms like a single crystal with respect to some desired property.

Impact resistance or flexibility can be measured using a variety ofconventional methods known to those skilled in the art. The flexibilityof the materials can be measured by the Gardner Impact Test using aGardner Variable Impact Tester in accordance with ASTM-D 5420-04, whichconsists of a 40-inch (101.6 cm) aluminum tube in which an 8- or 16-lb(17.6- or 35.2-kg) weight is dropped from various heights onto a metaldart resting onto the substrate being tested (2 inch by 2 inch by ⅛ inch(5.1 cm by 5.1 cm by 0.3 cm) specimen size. In a non-limitingembodiment, the impact strength results of the Gardner Impact Test of atleast about 65 in-lb (7.3 Joules) or from about 65 in-lb (7.3 Joules) toabout 640 in-lb (72 joules).

In another embodiment, the impact resistance can be measured using theDynatup Test in accordance with ASTM-D 3763-02 can be conducted whichconsists of a high velocity test with a load cell which measures totalenergy absorption in the first microseconds of the impact. The impactstrength can be measured in Joules. In a non-limiting embodiment, thesubstrate can have an impact strength of at least about 35 Joules orfrom about 35 to about 105 Joules.

Group P

In some non-limiting embodiments, the present invention providespolyurethane powder coating compositions. The powder coatingcompositions can be prepared from any of the polyurethanes orpoly(ureaurethane)s of Groups A-N discussed in detail above.

In some non-limiting embodiments, the present invention provides methodsof preparing a polyurethane powder coating composition comprising thesteps of: reacting at least one polyisocyanate with at least onealiphatic polyol to form a generally solid, hydroxy functionalprepolymer; melting the hydroxy functional prepolymer; melting at leastone generally solid polyisocyanate to form a melted polyisocyanate;mixing the melted hydroxy functional prepolymer and meltedpolyisocyanate to form a mixture; and solidifying the mixture to form agenerally solid powder coating composition.

The generally solid, hydroxy functional prepolymer can be prepared byreacting the polyisocyanate(s) with excess aliphatic polyol(s) andcatalyst in amounts as described above and heating the prepolymer to atemperature of about 140° C. or about 150° C. to about 180° C. for about1 to about 24 hours to facilitate essentially complete reaction of thecomponents and formation of a generally solid prepolymer.

In some non-limiting embodiments, the polyisocyanate is branched or atrimer as discussed above and the aliphatic polyol is an aliphatic diolhaving from 4 to 18 carbon atoms, or 4 or 5 carbon atoms, such aspropanediol, butanediol, cyclohexane dimethanol, 1,10-decanediol and/or1,12-dodecanediol. In other non-limiting embodiments, the polyisocyanatecan be any polyisocyanate as discussed above and the aliphatic polyolcan be a branched diol having from 4 to 18 carbon atoms, such astrimethylolpropane.

The equivalent ratio of isocyanate functional groups to hydroxylfunctional groups can range from about 1:0.9 to about 1:1.1, or about1:1.

The generally solid polyisocyanate can be melted by, for example,heating at a temperature of about 35° C. to about 150° C. for about 2 toabout 24 hours to form the melted polyisocyanate. The melted hydroxyfunctional prepolymer and melted polyisocyanate can be mixed andsolidified to form a generally homogeneous mixture suitable for forminga powder coating, as discussed below. The equivalent ratio of isocyanatefunctional groups of the polyisocyanate to hydroxyl functional groups ofthe hydroxy functional prepolymer can range from about 1.05:1 to about0.95:1, or about 1:1.

In other non-limiting embodiments, the present invention providesmethods of preparing a polyurethane powder coating compositioncomprising the steps of: reacting at least one polyisocyanate with atleast one aliphatic polyol to form a generally solid, hydroxy functionalprepolymer; dissolving the hydroxy functional prepolymer in a firstsolvent to form a first solution; dissolving at least one generallysolid polyisocyanate in a second solvent that is the same as orcompatible with the first solvent to form a second solution; mixing thefirst and second solutions; and removing substantially all of thesolvent to form a generally solid powder coating composition.

In some non-limiting embodiments, the polyisocyanate(s) are branched ora trimer as discussed above and the aliphatic polyol is an aliphaticdiol having from 4 to 18 carbon atoms, or 4 or 5 carbon atoms, such aspropanediol and/or butanediol. In other non-limiting embodiments, thepolyisocyanate can be any polyisocyanate as discussed above and thealiphatic polyol can be a branched diol having from 4 to 18 carbonatoms, such as trimethylolpropane.

The generally solid, hydroxy functional prepolymer can be prepared byreacting the polyisocyanate(s) with excess aliphatic polyol(s) andcatalyst in types and amounts as described above. The hydroxy functionalprepolymer is dissolved in a first solvent to form a first solution. Thesolvent can be any solvent capable of dissolving the hydroxy functionalprepolymer, such as a dipolar aprotic solvent, for example m-pyrole(N-methyl-2-pyrrolidone), N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulfoxide (DMSO), methylene chloride, dichlorobutane,cyclohexanone, dimethyl formamide and/or acetonitrile solvent. Theamount of solvent can range from about 20 to about 95 weight percentbased upon weight of solids of the hydroxy functional prepolymer.

The generally solid polyisocyanate in a second solvent that is the sameas or compatible with the first solvent to form a second solution. Thesolvent can be any solvent capable of dissolving the generally solidpolyisocyanate, such as a dipolar aprotic solvent, for example m-pyrole(N-methyl-2-pyrrolidone), N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulfoxide (DMSO), methylene chloride, dimethyl formamide and/oracetonitrile solvent. The amount of solvent can range from about 20 toabout 95 weight percent based upon weight of the solids ofpolyisocyanate.

The first and second solutions are mixed and substantially all of thesolvent is removed, for example by vacuum in an oven, to form agenerally solid powder suitable for use as a coating composition. Thepowder can be milled or micronized, if desired.

Curable powder coating compositions useful in the present invention aretypically prepared by first dry blending the polymer, e.g., polyurethaneor poly(ureaurethane) polymer, the crosslinking agent (if present), theparticles and additives, such as degassing agents, flow control agentsand catalysts, in a blender, e.g., a Henshel blade blender. The blenderis operated for a period of time sufficient to result in a homogenousdry blend of the materials charged thereto. The homogeneous dry blend isthen melt blended in an extruder, e.g., a twin screw co-rotatingextruder, operated within a temperature range sufficient to melt but notgel the components.

Optionally, curable powder coating compositions of the present inventionmay be melt blended in two or more steps. For example, a first meltblend is prepared in the absence of a cure catalyst. A second melt blendis prepared at a lower temperature, from a dry blend of the first meltblend and the cure catalyst. The melt blended curable powder coatingcomposition is typically milled to an average particle size of from, forexample, 15 to 30 microns.

Alternatively, the powder coating compositions of the present inventioncan be prepared by blending and extruding the ingredients as describedabove, but without the particles. The particles can be added as apost-additive to the formulation by simply mixing the particles into themilled powder coating composition, such as by mixing using a Henschelmixer. In some non-limiting embodiments, the powder coating compositionis slurried in a liquid medium, such as water, which may be sprayapplied.

Group Q

In some non-limiting embodiments, the compositions of the presentinvention can further comprise one or more types of reinforcingmaterials. These reinforcing materials can be present in any physicalform desired, for example as particles, including but not limited tonanoparticles, agglomerates, fibers, chopped fibers, mats, etc.

The reinforcing materials can be formed from materials selected from thegroup consisting of polymeric inorganic materials, nonpolymericinorganic materials, polymeric organic materials, nonpolymeric organicmaterials, composites thereof and mixtures thereof that are chemicallydifferent from the polyurethane or poly(ureaurethane). As used herein,“chemically different” from the polyurethane or poly(ureaurethane) meansthat the reinforcing material has at least one different atom or has adifferent arrangement of atoms compared to the polyurethane orpoly(ureaurethane).

As used herein, the term “polymeric inorganic material” means apolymeric material having a backbone repeat unit based on an element orelements other than carbon. See James Mark et al., Inorganic Polymers,Prentice Hall Polymer Science and Engineering Series, (1992) at page 5,incorporated by reference herein. Moreover, as used herein, the term“polymeric organic materials” means synthetic polymeric materials,semisynthetic polymeric materials and natural polymeric materials, allof which have a backbone repeat unit based on carbon.

An “organic material,” as used herein, means carbon-containing compoundswherein the carbon is typically bonded to itself and to hydrogen, andoften to other elements as well, and excludes binary compounds such asthe carbon oxides, the carbides, carbon disulfide, etc.; such ternarycompounds as the metallic cyanides, metallic carbonyls, phosgene,carbonyl sulfide, etc.; and carbon-containing ionic compounds such asmetallic carbonates, for example calcium carbonate and sodium carbonate.See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed.1993) at pages 761-762, and M. Silberberg, Chemistry The MolecularNature of Matter and Change (1996) at page 586, which are incorporatedby reference herein.

As used herein, the term “inorganic material” means any material that isnot an organic material.

As used herein, the term “composite material” means a combination of twoor more differing materials. For example a composite particle can beformed from a primary material that is coated, clad or encapsulated withone or more secondary materials to form a composite particle that has asofter surface. In some non-limiting embodiments, particles formed fromcomposite materials can be formed from a primary material that iscoated, clad or encapsulated with a different form of the primarymaterial. For more information on particles useful in the presentinvention, see G. Wypych, Handbook of Fillers, 2nd Ed. (1999) at pages15-202, incorporated by reference herein.

The reinforcing materials suitable for use in the compositions of theinvention can comprise inorganic elements or compounds known in the art.Suitable nonpolymeric, inorganic reinforcing materials can be formedfrom ceramic materials, metallic materials, and mixtures of any of theforegoing. Nonpolymeric, inorganic materials useful in forming thereinforcing materials of the present invention comprise inorganicmaterials selected from the group consisting of graphite, metals,oxides, carbides, nitrides, borides, sulfides, silicates, carbonates,sulfates, and hydroxides. Suitable ceramic materials comprise metaloxides, metal nitrides, metal carbides, metal sulfides, metal silicates,metal borides, metal carbonates, and mixtures of any of the foregoing.Non-limiting examples of suitable metals include molybdenum, platinum,palladium, nickel, aluminum, copper, gold, iron, silver, alloys, andmixtures of any of the foregoing. Non-limiting examples of metalnitrides are, for example, boron nitride; non-limiting examples of metaloxides are, for example, zinc oxide; non-limiting examples of suitablemetal sulfides are, for example, molybdenum disulfide, tantalumdisulfide, tungsten disulfide, and zinc sulfide; non-limiting examplesof metal silicates are, for example aluminum silicates and magnesiumsilicates such as vermiculite. In some non-limiting embodiments, thereinforcing material is essentially free of (less than 5 weight percentor less than 1 weight percent) or free of fillers such as sodiumcarbonate, calcium carbonate, silicates, alginates, carbon black, andmetal oxides such as titanium dioxide, silica, and zinc oxide.

In some non-limiting embodiments, the reinforcing materials can comprisea core of essentially a single inorganic oxide such as silica incolloidal, fumed, or amorphous form, alumina or colloidal alumina,titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria,zirconia, e.g., colloidal or amorphous zirconia, and mixtures of any ofthe foregoing; or an inorganic oxide of one type upon which is depositedan organic oxide of another type. In some non-limiting embodiments, thereinforcing materials should not seriously interfere with the opticalproperties of the cured composition. As used herein, “transparent” meansthat the cured coating has a BYK Haze index of less than 50 as measuredusing a BYK/Haze Gloss instrument.

The composition can comprise precursors suitable for forming silicaparticles in situ by a sol-gel process. The composition according to thepresent invention can comprise alkoxy silanes which can be hydrolyzed toform silica particles in situ. For example tetraethylortho silicate canbe hydrolyzed with an acid such as hydrochloric acid and condensed toform silica particles. Other useful particles include surface-modifiedsilicas such as are described in U.S. Pat. No. 5,853,809 at column 6,line 51 to column 8, line 43, incorporated herein by reference.

Sols, such as an organosols, of reinforcement particles can be used inthe present invention. These sols can be of a wide variety ofsmall-particle, colloidal silicas having an average particle size inranges such as are described below. The colloidal silicas can be surfacemodified during or after the particles are initially formed. Thesesurface modified silicas may contain on their surface chemically bondedcarbon-containing moieties, as well as such groups as anhydrous SiO₂groups and SiOH groups, various ionic groups physically associated orchemically bonded within the surface of the silica, adsorbed organicgroups, or combinations of any of the foregoing, depending on thecharacteristics of the particular silica desired. Such surface modifiedsilicas are described in detail in U.S. Pat. No. 4,680,204, incorporatedby reference herein. Such small particle colloidal silicas are readilyavailable, are essentially colorless and have refractive indices whichpermit their inclusion in compositions that, without additional pigmentsor components known in the art to color and/or decrease the transparencyof such compositions, result in colorless, transparent compositions orcoatings.

Other suitable non-limiting examples of reinforcing materials includecolloidal silicas, such as those commercially available from NissanChemical Company under the trademark ORGANOSILICASOLS™ such asORGANOSILICASOL™ MT-ST, and from Clariant Corporation as HIGHLINK™;colloidal aluminas, such as those commercially available from NalcoChemical under the trademark NALCO 8676®; and colloidal zirconias, suchas those commercially available from Nissan Chemical Company under thetrademark HIT-32M®.

In some non-limiting embodiments of the present invention, thereinforcing material is a nanostructure. As used herein, the term“nanostructure” refers to a three dimensional object wherein the lengthof the longest dimension ranges from 1 nm to 1000 nm, for example, from1 nm to 500 nm, or from 1 nm to 100 nm, or from 1 to 40 nm.

Nanostructural reinforcing materials can be incorporated into the matrixof a polymer by dispersing pre-made nanostructures, such as for examplenanoclays, into the polymer solution. Alternatively or additionally,nanostructural reinforcement materials can be incorporated into thepolymer matrix by forming the nanostructures in situ. For example, thenanostructural reinforcement materials can be formed in situ by mixing aprecursor solution for the polyurethane or poly(ureaurethane) with aprecursor for the nanostructures to form a mixture, formingnanostructures in the matrix of the polymer from the precursor of thenanostructures, and forming a polymer from the precursor solution of thepolymer.

As used herein, the phrase “precursor solution for the polyurethane orpoly(ureaurethane)” refers to any material that can be used as astarting material to form the polyurethane or poly(ureaurethane), asdiscussed above. For example, if the desired end product is an aliphaticpolyurethane, suitable precursors for the polymer include, but are notlimited to, 1,4-butanediol, trimethylolpropane, andbis(4-isocyanatocyclohexyl)methane and thiodiethanol.

As used herein, the phrase “precursor for the nanostructures” refers toany material that can be used as a starting material to form thenanostructures.

In some non-limiting embodiments of the invention, a solvent such aswater, ethanol, iso-propanol, butanol, etc. is added to the mixture.

The nanostructures are formed while the viscosity of the polymer is lowso that the nanostructures can incorporate themselves into the matrix ofthe polymer. The formation of the nanostructures can be initiated usingvarious techniques. In a non-limiting embodiment of the invention, thenanostructures are formed by adjusting the pH of the mixture. An acid orbase, such as ammonia, can be used to adjust the pH of the solution.Depending on the exact precursor solution of the polymer and the exactprecursor for the nanostructures, there is an optimum pH range in whichthe nanostructures will form. One of ordinary skill in the art wouldknow what the optimum pH range is based on both precursors.

In another non-limiting embodiment, the mixture can be heated toinitiate the formation of the nanoparticles. The mixture can be heatedto any temperature provided the mixture is not heated to a temperatureabove that at which the precursor solution would break down. Forexample, a precursor solution comprising polyurethane orpoly(ureaurethane) cannot be heated above 200° C. because that is thetemperature at which polyurethane or poly(ureaurethane) begins todecompose. Similarly to the pH range, the optimum temperature range atwhich the particles will form depends on the exact precursor solution ofthe polyurethane or poly(ureaurethane) and the exact precursor for thenanostructures. One of ordinary skill in the art would know what theoptimum temperature range is based on both precursors. Generally, thehigher the temperature to which the mixture is heated and/or the longerthe mixture is heated, the larger the size of the nanostructures thatwill be formed.

In yet another non-limiting embodiment of the invention, forming thenanostructures is accomplished by heating the mixture after the pH ofthe mixture is adjusted. In a further non-limiting embodiment of theinvention, forming the nanostructures is accomplished by heating themixture and then adjusting the pH of the mixture.

In various other non-limiting embodiments of the invention, thenanostructures can be formed by using one or more of the following:increasing the pressure on the mixture; by changing the concentration ofthe precursor solution for the polyurethane or poly(ureaurethane); byusing an initiator for nanostructure formation; and by seeding (addingno greater than 5% of the desired nanostructure material based on theprojected weight of the formed nanostructures as is well known in theart).

The formed nanostructures are charged species. If the pH of the solutionwas adjusted to cause the formation of the nanostructures, the charge isa result of the pH adjustment. If no pH adjustment was performed duringthe nanostructure formation step, a polymeric stabilizer such as, butnot limited to, sodium polymethacrylate in water and ammoniumpolymethacrylate in water, which are both commercially available asDarvan® 7 and as Darvan® C, respectively, from R.T. Vanderbilt Company,Inc. in Norwalk, Conn. can be added to the solution to create thecharge.

The third step involves forming the polyurethane or poly(ureaurethane)from a mixture including the precursor solution of the polyurethane orpoly(ureaurethane). The formation of the polyurethane orpoly(ureaurethane) can be initiated using various techniques (asdiscussed in detail above) based on the precursor solution of thepolyurethane or poly(ureaurethane) and the precursor for thenanostructures.

In another embodiment of the present invention, the second and thirdsteps described above are switched.

The method of making polymers having nanostructures incorporated intothe matrix of the polymer according to the present invention is referredto as an “in-situ” process. This means the nanostructures are formedduring the same process that produces the polymer as opposed topre-formed nanostructures being dispersed into a polymer solution.

During some methods of the present invention, ions (cations and/oranions) can form in the mixture. The formed ions and other processvariables, such as the pressure of the system in which the mixture isheld, can affect the final polymer. For example, the amount ofnanostructure formation and the morphology of the nanostructures willvary depending on the types and amount of ions present in the solution.

In the polymer matrix, the nanostructures typically continually approachone another and collide because they possess kinetic energy. Undernormal circumstances, some of the nanostructures would become boundtogether and agglomerate due to various forces such as Van der Waalsforces. As discussed above, agglomeration is not desirable because thenanostructures can effectively become regular sized particles and thedesired effect of incorporating the nanostructures is reduced.

However, the methods described above can produce polymers havingnanostructures in the matrix of the polymer that do not agglomerate tothe extent that the performance of the polymer is compromised, forexample to improve the thermal stability of polymer and/or to decreasethe chemical activity of polymer. The nanostructures do not agglomeratebecause they are stabilized. The stabilization can occur viaelectrostatic stabilization and/or steric stabilization.

Because the nanostructures in the polymer matrix are similarly chargedspecies, they repel each other. This prevents the nanostructures fromcoming so close together that they agglomerate. This phenomenon isreferred to as electrostatic stabilization.

Because the nanostructures are surrounded by polymer precursor solutionwhen they are formed, the nanostructures lose a degree of freedom whichthey would otherwise possess as the nanostructures approach each other.This loss of freedom is expressed, in thermodynamic terms, as areduction in entropy, which provides the necessary barrier to hinderagglomeration. This phenomenon is referred to as steric stabilization.The same principle applies when the method involves forming the polymerbefore forming the nanostructures.

The concentration of the nanostructures in the polymer matrix can rangefrom 0.1% to 90%, for example from 3% to 85% or from 15% to 80% based ontotal volume. The nanostructures in the polymer matrix can have thefollowing shapes: spherical, polyhedral-like cubic, triangular,pentagonal, diamond shaped, needle shaped, rod shaped, disc shaped etc.The nanostructures in the polymer matrix can have an aspect ratio of 1:1to 1:1,000, for example 1:1 to 1:100.

Non-limiting examples of suitable nanostructure materials includetitania, alumina, indium tin oxide (ITO), antimony tin oxide (ATO),monobutyl tin tri-chloride, indium acetate, and antimony tri-chloridenanostructures incorporated into the polymer matrix is formed. Suitableprecursors for titania nanostructures include, but are not limited to,titanium iso-propoxide, titanium (IV) chloride and potassium titanyloxalate. Suitable precursors for alumina nanostructures include, but arenot limited to, aluminum iso-propoxide, aluminum tri-tert-butoxide,aluminum tri-sec-butoxide, aluminum triethoxide, and aluminumpentanedionate. Suitable precursors for zirconia nanostructures include,but are not limited to, zirconium iso-propoxide, zirconiumtert-butoxide, zirconium butoxide, zirconium ethoxide, zirconium2,4-pentanedionate, and zirconium trifluoropentane-dionate.

In the first step, a precursor solution for polyurethane orpoly(ureaurethane) is mixed with a precursor for the nanostructures.

In the second step, nanostructures are formed from the precursor of thenanostructures in the polymer matrix. The nanostructure formation can becaused by adjusting the pH of the mixture followed by heating. The pHcan be adjusted by introducing an agent, such as ammonia, into themixture. For ITO nanostructures in a urethane or ureaurethane aqueoussolution, the nanostructures begin to form at a pH>8. After the pH isadjusted, the mixture is heated to a temperature of up to 100° C.Heating the solution to a temperature greater than 100° C. may cause thepolymer matrix to decompose. As discussed above, heating the mixture fora longer time period can increase the size of the nanostructures.

In the third step, the precursor solution for the polymer is convertedto the polymer, as discussed′above for forming the polyurethane andpoly(ureaurethane).

In a non-limiting embodiment of the invention, the final reinforcedpolymer is used as an interlayer in a laminated glass transparency forautomotive and architectural applications. As is well known in the art,a laminated glass transparency can be manufactured by interposing aninterlayer between at least two transparent glass sheets.

In this particular embodiment of the invention, a laminated glasstransparency for an automotive and architectural applicationsembodiment, it is important that the nanostructures do not agglomerate.If the nanostructures were to agglomerate and effectively achieve adiameter of greater than 200 nm, the nanostructures would scattervisible light rays to such an extent that transmittance through theinterlayer would be insufficient for the application. A polymer withnanostructures having an acceptable size for the application, can bedetermined using a “haze value”. The haze value is associated with thedegree to which transparency is prevented. The larger the nanostructurespresent in the polymer matrix, the higher the haze value. According tothe present invention, laminated glass for automotive and architecturalapplications has a haze value of less than or equal to. about 1%, forexample, less than or equal to about 0.3%, or less than or equal toabout 0.2%, as measured using a Hazeguard System from BYK-Gardner inColumbia, Md.

In the embodiment where a polyurethane or poly(ureaurethane) is beingformed having titania nanostructures incorporated into the polymermatrix, the first step can comprise mixing titanium iso-propoxide with a1-10 wt % H₂O₂ solution and suitable polyurethane or poly(ureaurethane)precursors as discussed above. The H₂O₂ acts as an initiator for titaniananostructures; particularly, titania nanostructures in the anataseform. Optionally, polymers such as polyoxyethylene (20) sorbitanmonooleate commercially available as Tween® 80 from ICI Ltd.(Bridgewater, N.J.) can be added to the solution to help stabilize thetitania nanostructures.

In the second step, the titania nanostructures are formed from theprecursor by heating the mixture to a temperature of up to 100° C.

In the third step, the precursor solution for the polymer is convertedinto polyurethane or poly(ureaurethane) as discussed in detail above.

In a non-limiting embodiment of the invention, polyurethane orpoly(ureaurethane) having titania, alumina, or zirconia nanostructuresincorporated into the matrix of the polymer can be used as an opticallens. A polymer with nanostructures having an acceptable size foroptical lens applications can be determined using a “haze value”.According to the present invention, an optical lens has a haze value ofless than or equal to 0.5%, for example less than or equal to 0.2%, asmeasured using a Hazeguard System from BYK Gardner.

In a non-limiting embodiment of the invention, a polyurethane having ITOor ATO nanostructures incorporated into the polymer matrix is formed.Such a polymer can be formed in the following manner. In the first step,a precursor solution for the trimethylol propane, methylenebis(4-cyclohexylisocyanate) and thiodiethanol is mixed with a precursorfor ITO or ATO nanostructures.

A suitable precursor solution for the polyurethane is trimethylolpropane, methylene bis(4-cyclohexylisocyanate), thiodiethanol includes,but is not limited to, 1,4-butanediol. Suitable precursors for ITOnanostructures include monobutyl tin tri-chloride and indium acetate. Asuitable precursor for ATO nanostructures is antimony tri-chloride.

In the second step, ITO or ATO nanostructures are formed from theprecursor. The nanostructure formation can be caused by adjusting the pHof the solution by introducing an agent, such as ammonia, into themixture followed by heating the mixture. For ITO nanostructures, the ITOnanostructures start to form at pH>8. After the pH is adjusted, themixture is heated to a temperature of up to 100° C. As discussed above,heating the mixture for a longer time period can increase the size ofthe nanostructures.

In the third step, the 1,4-butanediol is mixed into trimethylol propane,methylene bis(4-cyclohexylisocyanate), thiodiethanol as is well known inthe art. For example, 1,4 butanediol, thiodiethanol, trimethylol propane(TMP), and DESMODUR® W can all be mixed into a vessel and heated to 180°F. The mixture is mixed under vacuum for approximately 15 minutes, andthen a tin catalyst, such as dibutyltindilaurate or bismuth carboxylate,is added to the mixture in a 25 ppm concentration. The mixture is thencast into a glass mold and cured for at least 20 hours at 250° F. (121°C.) to form the polyurethane.

In a non-limiting embodiment, trimethylol propane, methylenebis(4-cyclohexylisocyanate), thiodiethanol having ITO or ATOnanostructures incorporated into the polymer matrix is used to form ananti-static coating for aircraft windows. The polymer with thenanostructures has an elastic modulus that is greater than that of thestandard trimethylol propane, methylene bis(4-cyclohexylisocyanate)thiodiethanol without ITO/ATO nanoparticles.

In other non-limiting embodiments, the reinforcement material is ananostructural reinforcement material formed in situ by swelling thepolyurethane in a solvent comprising a precursor for the nanostructures,and forming nanostructures in the matrix of the polyurethane from theprecursor of the nanostructures. Non-limiting examples of suitablesolvents for mild swelling of the polymer include methanol, propyleneglycol methyl ether such as DOWANOL PM (commercially available from DowChemical Co. of Midland, Mich.), diacetone alcohol, 2-propanol,1-propanol and acetylpropanol.

A polymer with nanostructures having an acceptable size for the aircraftwindow application can be determined using a “haze value”. According tothe present invention, a laminated aircraft window has a haze value ofless than or equal to about 1%, for example less than or equal to about0.5%, as measured using a Hazeguard System from BYK Gardner.

In some non-limiting embodiments of the present invention, thereinforcing materials have a hardness value greater than the hardnessvalue of materials that can abrade a polymeric coating or a polymericsubstrate. Examples of materials that can abrade the polymeric coatingor polymeric substrate include, but are not limited to, dirt, sand,rocks, glass, carwash brushes, and the like. The hardness values of theparticles and the materials that can abrade the polymeric coating orpolymeric substrate can be determined by any conventional hardnessmeasurement method, such as Vickers or Brinell hardness, or can bedetermined according to the original Mohs' hardness scale whichindicates the relative scratch resistance of the surface of a materialon-a scale of one to ten. The Mohs' hardness values of severalnonlimiting examples of particles formed from inorganic materialssuitable for use in the present invention are given in Table 1 below.TABLE A Mohs' hardness Particle material (original scale) Boron nitride2¹ Graphite 0.5-1² Molybdenum disulfide 1³ Talc   1-1.5⁴ Mica 2.8-3.2⁵Kaolinite 2.0-2.5⁶ Gypsum 1.6-2⁷ Calcite (calcium carbonate) 3⁸ Calciumfluoride 4⁹ Zinc oxide 4.5¹⁰ Aluminum 2.5¹¹ Copper 2.5-3¹² Iron   4-5¹³Gold 2.5-3¹⁴ Nickel 5¹⁵ Palladium 4.8¹⁶ Platinum 4.3¹⁷ Silver 2.5-4¹⁸Zinc sulfide 3.5-4¹⁹¹K. Ludema, Friction, Wear, Lubrication, (1996) at page 27, incorporatedby reference herein.²R. Weast (Ed.), Handbook of Chemistry and Physics, CRC Press (1975) atpage F-22.³R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993)at page 793, incorporated by reference herein.⁴Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at page 1113,incorporated by reference herein.⁵Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at page 784,incorporated by reference herein.⁶Handbook of Chemistry and Physics at page F-22.⁷Handbook of Chemistry and Physics at page F-22.⁸Friction, Wear, Lubrication at page 27.⁹Friction, Wear, Lubrication at page 27.¹⁰Friction, Wear, Lubrication at page 27.¹¹Friction, Wear, Lubrication at page 27.¹²Handbook of Chemistry and Physics at page F-22.¹³Handbook of Chemistry and Physics at page F-22.¹⁴Handbook of Chemistry and Physics at page F-22.¹⁵Handbook of Chemistry and Physics at page F-22.¹⁶Handbook of Chemistry and Physics at page F-22.¹⁷Handbook of Chemistry and Physics at page F-22.¹⁸Handbook of Chemistry and Physics at page F-22.¹⁹R. Weast (Ed.), Handbook of Chemistry Physics, CRC Press (71.sup.stEd. 1990) at page 4-158

In some non-limiting embodiments, the reinforcing material can be formedfrom a primary material that is coated, clad or encapsulated with one ormore secondary materials to form a composite material that has a hardersurface. In other non-limiting embodiments, reinforcement particles canbe formed from a primary material that is coated, clad or encapsulatedwith a differing form of the primary material to form a compositematerial that has a harder surface.

In some non-limiting examples, inorganic particles formed from aninorganic material such as silicon carbide or aluminum nitride can beprovided with a silica, carbonate or nanoclay coating to form a usefulcomposite particle. In other nonlimiting examples, a silane couplingagent with alkyl side chains can interact with the surface of aninorganic particle formed from an inorganic oxide to provide a usefulcomposite particle having a “softer” surface. Other examples includecladding, encapsulating or coating particles formed from nonpolymeric orpolymeric materials with differing nonpolymeric or polymeric materials.One non-limiting example of such composite particles is DUALITE™, whichis a synthetic polymeric particle coated with calcium carbonate that iscommercially available from Pierce and Stevens Corporation of Buffalo,N.Y.

In some non-limiting embodiments, the particles are formed from solidlubricant materials. As used herein, the term “solid lubricant” meansany solid used between two surfaces to provide protection from damageduring relative movement and/or to reduce friction and wear. In somenon-limiting embodiments, the solid lubricants are inorganic solidlubricants. As used herein, “inorganic solid lubricant” means that thesolid lubricants have a characteristic crystalline habit which causesthem to shear into thin, flat plates which readily slide over oneanother and thus produce an antifriction lubricating effect. See R.Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) atpage 712, incorporated by reference herein. Friction is the resistanceto sliding one solid over another. F. Clauss, Solid Lubricants andSelf-Lubricating Solids (1972) at page 1, incorporated by referenceherein.

In some non-limiting embodiments, the particles have a lamellarstructure. Particles having a lamellar structure are composed of sheetsor plates of atoms in hexagonal array, with strong bonding within thesheet and weak van der Waals bonding between sheets, providing low shearstrength between sheets. A non-limiting example of a lamellar structureis a hexagonal crystal structure. Inorganic solid particles having alamellar fullerene (i.e., buckyball) structure can also be useful in thepresent invention.

Non-limiting examples of suitable materials having a lamellar structurethat are useful in forming the particles of the present inventioninclude boron nitride, graphite, metal dichalcogenides, mica, talc,gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, and mixturesof any of the foregoing. Suitable metal dichalcogenides includemolybdenum disulfide, molybdenum diselenide, tantalum disulfide,tantalum diselenide, tungsten disulfide, tungsten diselenide, andmixtures of any of the foregoing.

In some non-limiting embodiments, the reinforcing material can be glassfiber strands. The glass fiber strands are formed from glass filaments,a class of filaments generally accepted to be based upon oxidecompositions such as silicates selectively modified with other oxide andnon-oxide compositions. Useful glass filaments can be formed from anytype of fiberizable glass composition known to those skilled in the art,and include those prepared from fiberizable glass compositions such as“E-glass”, “A-glass”, “C-glass”, “D-glass”, “R-glass”, “S-glass”, andE-glass derivatives that are fluorine-free and/or boron-free. As usedherein, the term “fiberizable” means a material capable of being formedinto a generally continuous filament, fiber, strand or yarn. As usedherein, “E-glass derivatives” means glass compositions that includeminor amounts of fluorine and/or boron or can be fluorine-free and/orboron-free. Furthermore, as used herein, “minor amounts of fluorine”means less than 0.5 weight percent fluorine, or less than 0.1 weightpercent fluorine, and “minor amounts of boron” means less than 5 weightpercent boron, or less than 2 weight percent boron. Basalt and mineralwool are examples of other fiberizable glass materials useful in thepresent invention. Non-limiting examples of suitable non-glassfiberizable inorganic materials include ceramic materials such assilicon carbide, carbon, quartz, graphite, mullite, aluminum oxide andpiezoelectric ceramic materials. In some non-limiting embodiments, theglass filaments are formed from E-glass. Such compositions and methodsof making glass filaments therefrom are well known to those skilled inthe art, such glass compositions and fiberization methods are disclosedin K. Loewenstein, The Manufacturing Technology of Continuous GlassFibres, (3d Ed. 1993) at pages 30-44, 47-60, 115-122 and 126-135,incorporated by reference herein.

The glass fibers can have a nominal filament diameter ranging from about5.0 to about 30.0 micrometers (corresponding to a filament designationof D through Y). Typically, the glass fiber strands have a strandcoating composition which is compatible with the composition applied toat least a portion of surfaces of the glass fiber strands, such as anessentially dried residue. The glass fiber strand reinforcements can beused in chopped form, generally continuous strands, mats, etc.

The particles also can be hollow particles formed from materialsselected from polymeric and nonpolymeric inorganic materials, polymericand nonpolymeric organic materials, composite materials, and mixtures ofany of the foregoing. Non-limiting examples of suitable materials fromwhich the hollow particles can be formed are described above. In someembodiments, the hollow particles are hollow glass spheres.

In some non-limiting embodiments, the reinforcing materials can beformed from nonpolymeric, organic materials. Nonlimiting examples ofnonpolymeric, organic materials useful in the present invention include,but are not limited to, stearates (such as zinc stearate and aluminumstearate), diamond, carbon black, and stearamide.

In some non-limiting embodiments, the particles can be formed frominorganic polymeric materials. Nonlimiting examples of useful inorganicpolymeric materials include polyphosphazenes, polysilanes, polysiloxane,polygeremanes, polymeric sulfur, polymeric selenium, silicones, andmixtures of any of the foregoing. A non-limiting example of a particleformed from an inorganic polymeric material suitable for use in thepresent invention is TOSPEARL¹, which is a particle formed fromcross-linked siloxanes and is commercially available from ToshibaSilicones Company, Ltd. of Japan.¹ See R. J. Perry “Applications for Cross-Linked Siloxane Particles”Chemtech. February 1999 at pp. 39-44.

The particles can be formed from synthetic, organic polymeric materialsthat are chemically different from the polyurethane orpoly(ureaurethane). Nonlimiting examples of suitable organic polymericmaterials include, but are not limited to, thermoset materials andthermoplastic materials. Nonlimiting examples of suitable thermoplasticmaterials include thermoplastic polyesters such as polyethyleneterephthalate, polybutylene terephthalate, and polyethylene naphthalate,polycarbonates, polyolefins such as polyethylene, polypropylene, andpolyisobutene, acrylic polymers such as copolymers of styrene and anacrylic acid monomer, and polymers containing methacrylate, polyamides,thermoplastic polyurethanes, vinyl polymers, and mixtures of any of theforegoing.

In some non-limiting embodiments, the polymeric organic material is a(meth)acrylic polymer or copolymer comprising at least one functionalgroup selected from the group consisting of silane groups, carboxylgroups, hydroxyl groups and amide groups. In some non-limitingembodiments, these meth)acrylic polymer or copolymers can be present asnanofibers having a diameter up to about 5000 nm, such as about 5 toabout 5000 nm, or less than the wavelength of visible light, for example700 nanometers or less, such as about 50 to about 700 nanometers. Thefibers may have a ribbon shape and in this case diameter is intended tomean the largest dimension of the fiber. Typically the width of theribbon shaped fibers can be up to about 5000 nanometers, such as about500 to about 5000 nm and the thickness up to about 200 nm, such as about5 to about 200 nm. The fibers can be prepared by electrospinning aceramic melt, a polymer melt or a polymer solution.

Suitable (meth)acrylic polymers can be made by addition polymerizationof unsaturated polymerizable materials that contain silane groups,carboxyl groups, hydroxyl groups and amine or amide groups. Non-limitingexamples of useful silane groups include groups that have the structureSi—X_(n) (wherein n is an integer having a value ranging from 1 to 3 andX is selected from chlorine, alkoxy esters, and/or acyloxy esters). Suchgroups hydrolyze in the presence of water including moisture in the airto form silanol groups that condense to form —Si—O—Si— groups. The(meth)acrylic polymer can contain hydroxyl functionality, for example byusing a hydroxyl functional ethylenically unsaturated polymerizablemonomer such as hydroxyalkyl esters of (meth)acrylic acids having from 2to 4 carbon atoms in the hydroxyalkyl group. The (meth)acrylic polymeroptionally contains nitrogen functionality introduced fromnitrogen-containing ethylenically unsaturated monomers, such as amines,amides, ureas, imidazoles and pyrrolidones. Further discussion of such(meth)acrylic polymers and fiberizing methods are disclosed in U.S.patent application Ser. No. __/____ entitled “Transparent CompositeArticles” and U.S. patent application Ser. No. __/____ entitled“Organic-Inorganic Polymer Composites and Their Preparation by LiquidInfusion”, each filed concurrently herewith and incorporated byreference herein.

Non-limiting examples of suitable fiberizable organic materials includecotton, cellulose, natural rubber, flax, ramie, hemp, sisal and wool.Non-limiting examples of suitable fiberizable organic polymericmaterials include those formed from polyamides (such as nylon andaramids)(such as KEVLAR™ aramid fibers), thermoplastic polyesters (suchas polyethylene terephthalate and polybutylene terephthalate), acrylics(such as polyacrylonitriles), polyolefins, polyurethanes and vinylpolymers (such as polyvinyl alcohol). Non-glass fiberizable materialsuseful in the present invention and methods for preparing and processingsuch fibers are discussed at length in the Encyclopedia of PolymerScience and Technology, Vol. 6 (1967) at pages 505-712, which isspecifically incorporated by reference herein.

It is understood that blends or copolymers of any of the above materialsand combinations of fibers formed from any of the above materials can beused in the present invention, if desired. Moreover, the term strand canencompass at least two different fibers made from differing fiberizablematerials. As used herein, the term “fiberizable” means a materialcapable of being formed into a generally continuous filament, fiber,strand or yarn.

Suitable thermoplastic fibers can be formed by a variety of polymerextrusion and fiber formation methods, such as for example drawing, meltspinning, dry spinning, wet spinning and gap spinning. Such methods arewell known to those skilled in the art and further discussion thereof isnot believed to be necessary in view of the present disclosure. Ifadditional information is needed, such methods are disclosed inEncyclopedia of Polymer Science and Technology, Vol. 6 at 507-508.

Non-limiting examples of useful polyamide fibers include nylon fiberssuch as nylon 6 (a polymer of caprolactam), nylon 6,6 (a condensationproduct of adipic acid and hexamethylenediamine), nylon 12 (which can bemade from butadiene) and nylon 10, polyhexamethylene adipamide,polyamide-imides and aramids such as KEVLAR™, which is commerciallyavailable from E. I. duPont de Nemours, Inc. of Wilmington, Del.

Non-limiting examples of useful thermoplastic polyester fibers includethose composed of polyethylene terephthalate and polybutyleneterephthalate.

Non-limiting examples of useful fibers formed from acrylic polymersinclude polyacrylonitriles having at least about 35% by weightacrylonitrile units, or at least about 85% by weight, which can becopolymerized with other vinyl monomers such as vinyl acetate, vinylchloride, styrene, vinylpyridine, acrylic esters or acrylamide. SeeEncyclopedia of Polymer Science and Technology, Vol. 6 at 559-561.

Non-limiting examples of useful polyolefin fibers are generally composedof at least 85% by weight of ethylene, propylene, or other olefins. SeeEncyclopedia of Polymer Science and Technology, Vol. 6 at 561-564.

Non-limiting examples of useful fibers formed from vinyl polymers can beformed from polyvinyl chloride, polyvinylidene chloride,polytetrafluoroethylene, and polyvinyl alcohol.

Further non-limiting examples of thermoplastic fiberizable materialsbelieved to be useful in the present invention include fiberizablepolyimides, polyether sulfones, polyphenyl sulfones, polyetherketones,polyphenylene oxides, polyphenylene sulfides and polyacetals.

It is understood that blends or copolymers of any of the above materialsand combinations of fibers formed from any of the above materials can beused in the present invention, if desired. Also, the thermoplasticfibers can have an antistatic agent coated thereon.

Suitable reinforcing materials can include mats or fabrics comprised ofany of the fibers discussed above. An increasingly popular process forforming composites is by compression molding or stamping a moldablesheet of a thermoplastic resin reinforced with fibers such as a glassfiber mat, often referred to as glass mat thermoplastics or “GMT”. Thesecomposite sheets can be used to form articles such as automobilecomponents and housings for computers. An example of a commerciallysuccessful GMT sheet is the AZDEL® moldable composite sheet which isformed by extruding layers of polypropylene resin sheet with needledmats of continuous glass fiber strand. The AZDEL® composite sheet iscommercially available from Azdel, Inc. of Shelby, N.C.

For reinforcing a resin matrix material, U.S. Pat. Nos. 3,664,909,3,713,962 and 3,850,723 disclose fibrous mats of unstranded filamentswhich can be layered with reinforcing mats of fiber strands.

U.S. Pat. No. 4,847,140 discloses an insulation medium formed byneedling a loose layer of inorganic fibers, such as glass, bondedtogether by a carrier web which is a blend of inorganic and organicfibers, with the carrier web comprising up to about 10% by weightorganic fibers.

U.S. Pat. Nos. 4,948,661, 5,011,737, 5,071,608 and 5,098,624 disclosefiber reinforced thermoplastic molded products produced by intimatelyblending reinforcing glass fibers and thermoplastic fibers into a weband heating the web to the melting point of the thermoplastic fiberswhile applying pressure to the web to press the web into a consolidatedstructure.

A non-limiting example of a useful polypropylene spun-bonded fiber matis commercially available from Fiberweb N.A., Inc. of Simpsonville, S.C.

Nonlimiting examples of suitable thermoset reinforcement materialsinclude thermoset polyesters, vinyl esters, epoxy materials, phenolics,aminoplasts, thermoset polyurethanes, and mixtures of any of theforegoing. A specific, nonlimiting example of a synthetic polymericparticle formed from an epoxy material is an epoxy microgel particle.

The concentration of reinforcement particles present in the curedarticle or coating can be determined, if desired, by a variety ofanalysis techniques well known in the art, such as Transmission ElectronMicroscopy (“TEM”), Surface Scanning Electron Microscopy (“X-SEM”),Atomic Force Microscopy (“AFM”), and X-ray Photoelectron Spectroscopy.

In some non-limiting embodiments, the present invention is directed tocured compositions as previously described wherein the reinforcementparticles have an average particle size of less than about 100 micronsprior to incorporation into the composition, or less than about 50microns prior to incorporation into the composition. In othernon-limiting embodiments, the present invention is directed to curedcompositions as previously described wherein the reinforcement particleshave an average particle size ranging from about 1 to less than about1000 nanometers prior to incorporation into the composition, or about 1to about 100 nanometers prior to incorporation into the composition.

In other non-limiting embodiments, the present invention is directed tocured compositions as previously described wherein the particles have anaverage particle size ranging from about 5 to about 50 nanometers priorto incorporation into the composition, or about 5 to about 25 nanometersprior to incorporation into the composition.

In an embodiment where the average particle size of the particles is atleast about one micron, the average particle size can be measuredaccording to known laser scattering techniques. For example the averageparticle size of such particles is measured using a Horiba Model LA 900laser diffraction particle size instrument, which uses a helium-neonlaser with a wave length of 633 nm to measure the size of the particlesand assumes the particle has a spherical shape, i.e., the “particlesize” refers to the smallest sphere that will completely enclose theparticle.

In an embodiment of the present invention wherein the size of theparticles is less than or equal to one micron, the average particle sizecan be determined by visually examining an electron micrograph of atransmission electron microscopy (“TEM”) image, measuring the diameterof the particles in the image, and calculating the average particle sizebased on the magnification of the TEM image. One of ordinary skill inthe art will understand how to prepare such a TEM image, and adescription of one such method is disclosed in the examples set forthbelow. In one nonlimiting embodiment of the present invention, a TEMimage with 105,000× magnification is produced, and a conversion factoris obtained by dividing the magnification by 1000. Upon visualinspection, the diameter of the particles is measured in millimeters,and the measurement is converted to nanometers using the conversionfactor. The diameter of the particle refers to the smallest diametersphere that will completely enclose the particle.

The shape (or morphology) of the reinforcing material can vary dependingupon the specific embodiment of.the present invention and its intendedapplication. For example generally spherical morphologies (such as solidbeads, microbeads, or hollow spheres), can be used, as well as particlesthat are cubic, platy, or acicular (elongated or fibrous). Additionally,the particles can have an internal structure that is hollow, porous orvoid free, or a combination of any of the foregoing, e.g., a hollowcenter with porous or solid walls. For more information on suitableparticle characteristics see H. Katz et al. (Ed.), Handbook of Fillersand Plastics (1987) at pages 9-10, incorporated by reference herein.

It will be recognized by one skilled in the art that mixtures of one ormore particles having different average particle sizes can beincorporated into the compositions in accordance with the presentinvention to impart the desired properties and characteristics to thecompositions. For example particles of varying particle sizes can beused in the compositions according to the present invention.

In some non-limiting embodiments, the reinforcing material(s) arepresent in the composition in an amount ranging from about 0.01 to about75 weight percent, or about 25 to about 50 weight percent, based ontotal weight of the components which form the composition.

Reinforcement particles can be present in a dispersion, suspension oremulsion in a carrier. Nonlimiting examples of suitable carriersinclude, but are not limited to, water, solvents, surfactants, or amixture of any of the foregoing. Nonlimiting examples of suitablesolvents include, but are not limited to, mineral oil, alcohols such asmethanol or butanol, ketones such as methyl amyl ketone, aromatichydrocarbons such as xylene, glycol ethers such as ethylene glycolmonobutyl ether, esters, aliphatics, and mixtures of any of theforegoing.

Dispersion techniques such as grinding, milling, microfluidizing,ultrasounding, or any other dispersing techniques well known in the artof coatings or molded article formulation can be used. Alternatively,the particles can be dispersed by any other dispersion techniques knownin the art. If desired, the particles in other than colloidal form canbe post-added to an admixture of other composition components anddispersed therein using any dispersing techniques known in the art.

A further embodiment of the present invention is directed to a coatedautomobile substrate comprising an automobile substrate and a curedcomposition coated over at least a portion of the automobile substrate,wherein the cured composition is selected from any of the foregoingcompositions. In yet another embodiment, the present invention isdirected to a method of making a coated automobile substrate comprisingproviding an automobile substrate and applying over at least a portionof the automotive substrate a coating composition selected from any ofthe foregoing compositions. Again, the components used to form the curedcompositions in these embodiments can be selected from the componentsdiscussed above, and additional components also can be selected fromthose recited above.

Suitable flexible elastomeric substrates can include any of thethermoplastic or thermoset synthetic materials well known in the art.Nonlimiting examples of suitable flexible elastomeric substratematerials include polyethylene, polypropylene, thermoplastic polyolefin(“TPO”), reaction injected molded polyurethane (“RIM”), andthermoplastic polyurethane (“TPU”).

Nonlimiting examples of thermoset materials useful as substrates forcoating with compositions of the present invention include polyesters,epoxides, phenolics, polyurethanes such as “RIM” thermoset materials,and mixtures of any of the foregoing. Nonlimiting examples of suitablethermoplastic materials include thermoplastic polyolefins such aspolyethylene, polypropylene, polyamides such as nylon, thermoplasticpolyurethanes, thermoplastic polyesters, acrylic polymers, vinylpolymers, polycarbonates, acrylonitrile-butadiene-styrene (“ABS”)copolymers, ethylene propylene diene terpolymer (“EPDM”) rubber,copolymers, and mixtures of any of the foregoing.

Nonlimiting examples of suitable metal substrates useful as substratesfor coating with compositions of the present invention include ferrousmetals (e.g., iron, steel, and alloys thereof), nonferrous metals (e.g.,aluminum, zinc, magnesium, and alloys thereof, and mixtures of any ofthe foregoing. In the particular use of automobile components, thesubstrate can be formed from cold rolled steel, electrogaivanized steelsuch as hot dip electrogalvanized steel, electrogalvanized iron-zincsteel, aluminum, and magnesium.

When the substrates are used as components to fabricate automotivevehicles (including, but not limited to, automobiles, trucks andtractors) they can have any shape, and can be selected from the metallicand flexible substrates described above. Typical shapes of automotivebody components can include bodies (frames), hoods, doors, fenders,mirror housings, bumpers, and trim for automotive vehicles.

In embodiments of the present invention directed to automotiveapplications, the cured compositions can be, for example, theelectrodeposition coating, the primer coating, the basecoat and/or thetopcoat. Suitable topcoats include monocoats and basecoat/clearcoatcomposites. Monocoats are formed from one or more layers of a coloredcoating composition.

In some non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of Groups A-P can be reinforced with fiberglass toform a composite article, such as for example a windmill blade,blast-resistant panels, bullet resistant panels and radomes.

Group R

In some non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of Groups A-Q can be useful as one or more layers ina multilayer article. If desired, the multilayered article can belaminated.

In some non-limiting embodiments, the polymer is cut while warm,granulated, extruded and/or milled and calendered to sheets andassembled into laminates and aged for several days, a week, or longer atambient temperature (about 25° C.).

In some non-limiting embodiments, the present invention providesarticles having multiple layers of polyurethanes and/orpoly(ureaurethanes) of the present invention. The thickness of eachlayer and overall thickness of the article can vary as desired.Non-limiting examples of suitable thicknesses of the layers and articlesare discussed below. The layers can be laminated together, if desired.

In some non-limiting embodiments, the present invention providesmultilayered articles or laminates comprising: (a) at least one layer ofthe polyurethane(s) or poly(ureaurethane)s of the present invention asdiscussed above; and (b) at least one layer of a substrate selected fromthe group consisting of paper, glass, ceramic, wood, masonry, textile,metal or organic polymeric material and combinations thereof. In somenon-limiting embodiments, the layer (a) of polyurethane(s) orpoly(ureaurethane)s of the present invention is chemically or physicallydifferent from the organic polymeric material of layer (b), i.e., it hasat least one different atom, arrangement of atoms or configuration. Inother embodiments, two or more layers of the same or similarpolyurethane(s) or poly(ureaurethane)s of the present invention can beused.

In some non-limiting embodiments, the substrate is an optically clearpolymerized organic material prepared from a thermoplastic polycarbonateresin, such as the carbonate-linked resin derived from bisphenol A andphosgene, which is sold under the trademark LEXAN® by GE Plastics ofPittsfield, Massachusetts; a polyester, such as the material sold underthe trademark MYLAR by E.I. duPont de Nemours Co. of Wilmington, Del.; apoly(methyl methacrylate), such as the material sold under the trademarkPLEXIGLAS by Altuglas International of Philadelphia, Pa.;polyhexylene-polycarbonate-based polyurethanes; polymerizates of apolyol(allyl carbonate) monomer, especially diethylene glycol bis(allylcarbonate), which monomer is sold under the trademark CR-39 by PPGIndustries, Inc., and polymerizates of copolymers of a polyol (allylcarbonate), e.g., diethylene glycol bis(allyl carbonate), with othercopolymerizable monomeric materials, such as copolymers with vinylacetate, and copolymers with a polyurethane having terminal diacrylatefunctionality, as described in U.S. Pat. Nos. 4,360,653 and 4,994,208;and copolymers with aliphatic urethanes, the terminal portion of whichcontain allyl or acrylyl functional groups, as described in U.S. Pat.No. 5,200,483; poly(vinyl acetate), polyvinylbutyral, polyurethane,polymers of members of the group consisting of diethylene glycoldimethacrylate monomers, diisopropenyl benzene monomers, and ethoxylatedtrimethylol propane triacrylate monomers; cellulose acetate, cellulosepropionate, cellulose butyrate, cellulose acetate butyrate, polystyreneand copolymers of styrene with methyl methacrylate, vinyl acetate andacrylonitrile.

A non-limiting example of a suitable polyhexylene-polycarbonate-basedpolyurethane can be prepared as follows: a hydroxyl—terminatedprepolymer is made from 0.2 equivalents of a 1000 molecular weighthexanediol—based carbonate diol (PC-1733 commercially available fromStahl), 0.8 equivalents of 1,5 pentanediol, and 1.0 equivalents oftrimethylhexanediisocyanate. The components are heated to 180° F. (82°C.) and using 100 ppm of dibutyltin dilaurate as a catalyst. Theprepolymer has an equivalent weight of 218 grams/equivalent. Thetrimeric hydroxyl terminated prepolymer is dissolved into cyclohexanonesolvent and 1 equivalent of Desmodur 3390 (triisocyanurate trimer ofhexanediisocyanate) added as a crosslinker and mixed. The coatingsolution is 95% solids with a viscosity of 3000 centipoise. The solutioncan be flow-coated onto any bisphenol A polycarbonate such as Lexan andcured in an oven at 250° F. (121° C.) for 4 hours. The coating thicknesscan range from 2 to 5 mils thick and is elastomeric.

The number and thickness of the layers can vary as desired. For examplethe thickness of a single layer can range from about 0.1 mm to about 60cm, or about 2 mm to about 60 cm, or about 0.3 cm to about 2.5 cm. Thenumber of layers can range from 2 to 10, or 2 to 4, as desired. Theoverall thickness of the multilayer article or laminate can range fromabout 2 mm to about 15 cm or more, or about 2 mm to about 5 cm. Forballistics applications, the overall thickness of the polyurethane orpoly(ureaurethane) of the present invention can range from about 2 mm toabout 15 cm or more, or about 2 mm to about 5 cm. Also, for ballisticsapplications suitable substrates for layering with the polyurethane(s)and/or poly(ureaurethane)s of the present invention include polyesters,polycarbonates, or polyether thermoplastic elastomers, for example. Thelayer(s) of polyurethane or poly(ureaurethane) of the present inventioncan be positioned on the outside of the laminate (facing the potentialballistic impact), on the inside of the laminate, or elsewhere inbetween.

Groups A-R

In some non-limiting embodiments, polyurethanes and poly(ureaurethane)sof the present invention can have a hard segment content of about 10 toabout 100 weight percent, or about 20 to about 80 weight percent, orabout 30 to about 75 weight percent. Hard segment calculation isdiscussed in detail above.

In some non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of the present invention generally have a urethanecontent (Wu) of about 20 to about 40 weight percent, or about 21 toabout 36 weight percent, or about 30 to about 40 weight percent. Theurethane content is the percentage by weight of the urethane linkagespresent in the polymer and can be calculated by determining the totalnumber of equivalents, and from this the total weight of all reactants,and dividing the total weight of the urethane linkages obtainable fromthese reactants by the total weight of the reactants themselves. Thefollowing example will further explain the calculation. In Example I,Formulation 1 which follows, a polyurethane article according to theinvention was prepared by reacting 0.7 equivalents of 1,4-butanediol,0.3 equivalents of trimethylolpropane and one equivalent of4,4′-methylene-bis-(cyclohexyl isocyanate) (DESMODUR W). The equivalentweight of the 1,4-butanediol is 45, the equivalent weight of thetrimethylolpropane is 44.7 (corrected for impurities) and the equivalentweight of the DESMODUR W is 131.2. Therefore, the actual weight ofingredients used is 31.54 parts by weight of 1,4-butanediol, 13.2 partsby weight of trimethylolpropane and 131.2 parts by weight of DESMODUR Wor a total reactant weight of 175.9 parts by weight. One equivalent ofDESMODUR W will yield one equivalent of urethane linkage. The equivalentweight of a urethane linkage is 59 so that the total weight of theurethane linkages determined by multiplying the equivalent weight by thenumber of equivalents would also be 59. Thus, the total weight of theurethane linkage, 59, divided by the total weight of the reactants,175.9, multiplied by 100 to convert to percentages would give apercentage by weight of urethane linkage of 33.49 percent by weight.

In an analogous manner, the percentage by weight of cyclic structures(W_(c)) (such as for example cyclohexyl) can be calculated. In ExampleI, Formulation 1, the only material contributing cyclohexyl moieties isthe DESMODUR W. One equivalent of DESMODUR W would yield one equivalentof cyclohexyl moiety which has an equivalent weight of 81. Thus, thetotal weight of cyclohexyl moiety would be equal to 81 and this dividedby the total weight of reactants or 175.9 would yield a W_(c) of 46percent. In some non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of the present invention can have a cyclic contentof about 10 to about 80 weight percent, about 20-to about 70 weightpercent, about 30 to about 70 weight percent, or about 30 to about 60weight percent.

In some non-limiting embodiments, the resulting polyurethanes orpoly(ureaurethane)s of the present invention when cured can be solid,and essentially transparent. In some non-limiting embodiments, thepolyurethane can be partially cured or fully cured such that essentiallyno further reaction occurs.

In some non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of the present invention generally have a numberaverage molecular weight, as estimated from inherent viscositymeasurements, of at least about 20,000 grams/mole, or ranging from about20,000 to about 1,000,000 grams/mole, or ranging from about 20,000 toabout 800,000 grams/mole. The polyurethanes and poly(ureaurethane)s ofthe present invention generally have an average molecular weight percrosslink of at least about 500 grams per mole, in some embodimentsranging from about 500 and about 15,000 grams/mole, or ranging fromabout 1800 and about 15,000 grams/mole. The polyurethanes andpoly(ureaurethane)s of the present invention generally have a crosslinkdensity of at least about 11,000 grams per mole.

In some non-limiting embodiments, the polyurethane(s) andpoly(ureaurethane)s of the present invention when cured can have lowdensity. In some non-limiting embodiments, the density can be from atleast 0.9 to less than 1.25 grams/cm³, or from at least 1.0 to less than1.45 grams/cm³, or from 1.08 to 1.37 grams/cm³, or from 1.08 to 1.13. Insome non-limiting embodiments, the density of polyurethanes andpoly(ureaurethane)s of the present invention can be less than LEXAN(density about 1.21 g/cm³) and conventional stretched acrylic (densityabout 1.18 g/cm³). The density can be measured using a DensiTECHinstrument manufactured by Tech Pro, Incorporated. In some non-limitingembodiments, the density is measured in accordance with ASTM D 792-00.

Also, some optically clear polyurethanes and poly(ureaurethane)s uponheating can exhibit a low temperature exotherm at about −70° C.(differential thermal analysis can be determined using a du Pont 900thermal analyzer), and about 11° C., indicating that the polymers aregenerally amorphous.

In some non-limiting embodiments, softening points of about 65° C. toabout 200° C., melting points of about 80° C. to about 220° C., anddecomposition temperatures of about 280° C. to about 330° C. undernitrogen atmosphere are typical.

The polyurethanes and poly(ureaurethane)s of the present invention canbe used to form articles having good impact resistance or flexibility,high impact strength, high tensile strength, resistance to heatdistortion, good hardness, high Young's modulus, high K factor, goodsolvent resistance, good clarity or transparency, high lighttransmittance, low haze, good weatherability, good energy-absorption,good moisture stability, good ultraviolet light stability, and/or goodballistics resistance.

Non-limiting examples of suitable methods and equipment for measuringimpact resistance and impact strength are discussed in detail above.

In some embodiments, the heat distortion temperature of cured articlesof the invention can be at least about 190° F. (88° C.) or above about200° F. (93° C.), as determined according to ASTM-D-648.

Hardness of the polyurethanes and poly(ureaurethanes) can be determinedby the Shore hardness and accordingly, in some embodiments articles ofthe invention have a Shore D hardness at room temperature (25° C.) usinga Shore D durometer of at least about 75 or at least about 80.

Tensile strength at yield or break can be measured according to ASTM-D638-03. In some non-limiting embodiments, the tensile strength at yieldis at least about 6,800 lb/in² (47 MPa) according to ASTM-D 638-03, orabout 6,800 to about 20,000 lb/in² (about 47 to about 138 MPa), or about12,000 to about 20,000 lb/in² (about 83 to about 138 MPa).

Young's Modulus can be measured according to according to ASTM-D 638-03.In some non-limiting embodiments, the Young's Modulus is at least about215,000 lb/in² (about 1482 MPa), or about 215,000 (about 1482 MPa) toabout 600,000 lb/in² (about 4137 MPa), or about 350,000 (about 2413 MPa)to about 600,000 lb/in² (about 4137 MPa). For commercial airplane cabinwindow applications, when the cabin pressure is 10 psi (0.07 MPa) ormore greater than the external pressure, the cabin windows can deflectinto the airstream, thereby increasing noise and decreasing fuelefficiency. Higher values of Young's Modulus indicate increasedstiffness and less tendency for the window to deflect into theairstream. In some non-limiting embodiments for aircraft windowapplications, the values of Young's Modulus can be at least about350,000 (about 2413 MPa). In typical ballistics applications, the outerplies are glass, which is hard enough to deform a bullet by spreadingthe impact stress over a large area before it penetrates the underlyingplies. A poly(ureaurethane) prepared according to Example A, Formulation125 according to the present invention having a thickness of about 0.125inches (0.3 cm) flattened a 9 mm bullet fired at 1350 ft/sec (411 m/sec)from a distance of 20 feet (6.1 m). Though the ply broke into 2 crackedareas, it did not shatter over a large area like glass, which wouldprovide greater visibility for an occupant to escape attack on avehicle.

K factor is a measure of crack propagation. Crack propagation can bemeasured according to U.S. Dept. of Defense MIL-PRF-25690B (Jan. 29,1993). In some non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of the present invention have a K-Factor crackpropagation resistance of at least about 1000 lb/in^(3/2) (1,098,800N/m^(3/2)), or about 1000 lb/in^(3/2) (1,098,800 N/m^(3/2)) to about4000 lb/in^(3/2) (4,395,200 N/m^(3/2)), or about 2000 lb/in^(3/2)(2,197,600 N/m^(3/2)) to about 4000 lb/in^(3/2) (4,395,200 N/m^(3/2)).

Compositions suitable for use in automobile windshields meet thestandard requirement of minimum light transmission of 70 percent or 86.5percent or above (Illuminant A. Tungsten lamp 2,840° K.) and less than 2percent haze (ANSI CODE Z-26.1, 1966, Test No. 18). The percent lighttransmission and percent haze can be measured by a Hunter PivotableSphere Haze Meter according to ASTM E903-82.

The polyurethanes and poly(ureaurethane)s of the present invention canhave outstanding weather characteristics as measured by UV lightstability and hydrolytic stability. Fade-O-Meter® exposure can beconducted according to ASTM G-25-70, Method A using a Fade-O-Meter, TypeFDA-R, Serial No. F02951, manufactured by Atlas Electric Devices Co.,Chicago, Ill. The light source can a carbon arc lamp enclosed in a fusedsilica globe. The operating temperature of the Fade-O-Meter (blackpanel) can be 140° F. (60° C.) and the instrument operated with no waterin the atomizing unit. Sample sizes are 2½ inches by ⅛ inch (6.35 cm by15.24 cm by 0.32 cm). Weather-O-Meter® exposure can be conductedaccording to ASTM D-1499-64 using a Weather-O-Meter, Type DMC, SerialNo. WO-1305. The type of light source can be a twin carbon arc lampenclosed in a fused silica globe. The operating black panel temperaturecan be 140° F. (60° C.). The spray of water is deionized water at atemperature of about 70° F. (21° C.). The number and type of water spraynozzles which are used are four No. 50 nozzles. Alternatively, the UVresistance can be determined using QUV at 1000 hours according to ASTMG-53.

Abrasion resistance can be measured using a Taber Abrader having aCS-10F abrasion wheel with 500 grams of weight, for a sample size 3inches by 3 inches by ⅛ inch (7.62 cm by 7.62 cm by 0.32 cm) accordingto ASTM D 1044-99. In some non-limiting embodiments, 100 cycles of Tabercan result in 30% haze for stretched acrylic and from 5% to 40%, or from10% to 15% or less than about 5% for the polyurethanes andpoly(ureaurethane)s of the present invention.

The polyurethanes and poly(ureaurethane)s of the present invention canhave good craze resistance to solvents and acids. Craze resistance canbe measured according to U.S. Dept. of Defense MIL-PRF-25690B (Jan. 29,1993). Non-limiting examples of solvents and acids for Stress CrazeTesting include methanol, isopropanol, ethylene glycol, propyleneglycol, ethyl acetate, acetone, toluene, isobutyl acetate, Skydrol(hydraulic fluid), jet fuel such as JP-4, and 75% aqueous solution ofsulfuric acid. In some non-limiting embodiments, uncoated articlesprepared from the polyurethanes and poly(ureaurethane)s of the presentinvention have a stress craze resistance in organic solvent and 75% byweight aqueous solution of sulfuric acid of at least about 1000 psi (6.9MPa) tensile stress, or about 1000 psi (6.9 MPa) to about 4000 psi (27.6MPa), or about 2000 psi (13.8 MPa) to about 4000 psi (27.6 MPa). In somenon-limiting embodiments, the polyurethanes and poly(ureaurethane)s ofthe present invention when uncoated can withstand 75% sulfuric acid forup to thirty days or any organic solvent at between 1000 psi (6.9 MPa)and 4000 psi (27.6 MPa) membrane stress.

In some non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of the present invention when polymerized canproduce a polymerizate having a refractive index of at least 1.55, or atleast 1.56, or at least 1.57, or at least 1.58, or at least 1.59, or atleast 1.60, or at least 1.62, or at least 1.65. In other non-limitingembodiments, the poly(ureaurethane)s of the present invention whenpolymerized can produce a polymerizate having an Abbe number of at least32, or at least 35, or at least 38, or at least 39, or at least 40, orat least 44. The refractive index and Abbe number can be determined bymethods known in the art such as American Standard Test Method (ASTM)Number D 542-00. Further, the refractive index and Abbe number can bedetermined using various known instruments. In a non-limiting embodimentof the present invention, the refractive index and Abbe number can bemeasured in accordance with ASTM D 542-00 with the following exceptions:(i) test one to two samples/specimens instead of the minimum of threespecimens specified in Section 7.3; and (ii) test the samplesunconditioned instead of conditioning the samples/specimens prior totesting as specified in Section 8.1. Further, in a non-limitingembodiment, an Atago, model DR-M2 Multi-Wavelength Digital AbbeRefractometer can be used to measure the refractive index and Abbenumber of the samples/specimens.

Solid articles that can be prepared using the polyurethanes orpoly(ureaurethanes) of the present invention include but are not limitedto optical articles or lenses, photochromic articles or lenses, windows,transparencies, such as generally transparent windows, windshields,sidelights and backlights, aircraft transparencies, ballistic resistantarticles, windmill components such as blades, and glazings.

In some non-limiting embodiments, the polymeric substrate materialincluding the coating composition applied thereto may be in the form ofoptical elements such as windows, pIano and vision correcting ophthalmiclenses, exterior viewing surfaces of liquid crystal displays, cathoderay tubes e.g., video display tubes for televisions and computers, clearpolymeric films, transparencies, e.g., windshields, aircrafttransparencies, plastic sheeting, etc.

The polyurethanes and poly(ureaurethane)s of the present invention aredesirable for a wide variety of uses. They are particularly useful asglazing materials for aircraft safety glass windows. Besides aircraftglazing, the polyurethanes and poly(ureaurethane)s of the invention insheet form can be used in architectural applications and can be tintedor made opaque by pigmenting if desired. In such applications, thepolyurethanes and poly(ureaurethane)s of the invention can be in sheetform and may be used alone or laminated to other materials as discussedabove. The layers in the composite can have the same or differentmodulus values, as desired. Also, in some embodiments the polyurethanesand poly(ureaurethane)s of the invention can be used for optical lensessince they can be optically clear, unaffected by ultraviolet light andhumidity exposure and abrasion resistant.

In other non-limiting embodiments, the polyurethanes andpoly(ureaurethane)s of the present invention can be used as low thermalexpansion substrates for deposition of conductive films forelectrochromic applications, microwave absorbing films or low resistancefilms. In other non-limiting embodiments, a stretched acrylic substratecan be coated with a cyanoethyl acrylate/acrylic copolymer and furthercoated with the polyurethanes and poly(ureaurethane)s of the presentinvention.

The polyurethanes and poly(ureaurethane)s of the invention can be usedin sheet form and can vary in thickness from about 2 to 500 mils,although somewhat thinner and thicker sheets can be used, depending uponthe application. For aircraft use, in some embodiments the thickness canvary between ⅛ inch and ½ inch (0.32 cm to 1.27 cm).

In some embodiment, an automobile window can be prepared from athermoplastic polycarbonate resin, such as that sold under the trademarkLEXAN, with the coating composition of the present invention applied asa weather layer on the outboard side of the window to increase theweatherability of the window. Alternatively, an automobile window can beprepared as a glass/LEXAN laminate, with the glass as the outboard layerand the coating composition of the present invention applied as a layeron the inboard side of the laminate.

The coating composition of the present invention can be applied to thesubstrate surface using any known coating procedures. Desirably, thecoating composition is flow coated over the substrate surface by anautomated flow-coating system in which the surface tension of the liquidpulls a coherent sheet of liquid across the substrate surface as themechanical flow-coating device traverses across the substrate sheet. Anautomatic flow-coating device typically consists of an articulating armthat holds a nozzle connected to a pressure pot where the resin solutionis held. The arm runs on a track above the sheet to be coated. The rateof flow of the liquid is adjusted using the pressure pot. The rate oftraverse of the articulating arm is set using a potentiometer. Thenozzle distance from the sheet is optimized and kept constant, via thearticulating arm. This is particularly important for curved sheets. Thethickness of the coating is determined by the initial viscosity of theresin solution and the rate of solvent evaporation. The evaporation rateis mainly controlled by the solvent choice and the cubic feet/minuteairflow in the ventilated coating booth. Alternatively, the coatingcompositions can be prepared and cast in an appropriate mold to form adesired structure, which can then be applied as a layer to a suitablesubstrate, such as through a lamination process, or may used as amonolithic structure.

The coating composition generally may be applied to a substrate byitself as a transparent or pigmented monocoat, or as the pigmented basecoat and/or transparent topcoat in a color-plus-clear composite coatingas known to those skilled in the art. In some embodiments, the coatingcan be applied before the isocyanate and hydroxyl groups are fullyreacted, for example by spraying the isocyanate and hydroxyl componentsseparately through a mixing nozzle to apply the coating to thesubstrate. Alternatively, the coating can be partially cured in an ovenand then subjected to a high moisture environment, such as high humidityor water spray, to further react and cure the coating. If desired, thecoating composition may contain additional materials well known in theart of formulated surface coatings, such as surfactants, flow controlagents, thixotropic agents, fillers, antigassing agents, organiccosolvents, catalysts, and other customary auxiliaries. These materialscan constitute up to 40 percent by weight of the total weight of thecoating composition.

As aforementioned, although the cured compositions can be formed fromliquid coating compositions, they also can be formed from coatingcompositions formulated as powder coating compositions.

In another non-limiting embodiment, the cured compositions of thepresent invention also can be useful as decorative or protectivecoatings for pigmented plastic (elastomeric) substrates or mold-in-color(“MIC”) plastic substrates. In these applications, the compositions canbe applied directly to the plastic substrate or included in the moldingmatrix. Optionally, an adhesion promoter can first be applied directlyto the plastic or elastomeric substrate and the composition applied as atopcoat thereover.

In another non-limiting embodiment, the compositions of the presentinvention also can be useful as spalling shield layer, anti-lacerativecoating layer or break-in resistant coating layer for glass or othersubstrates.

In a non-limiting embodiment, the polyurethane polymerizate of thepresent invention can be used to prepare photochromic articles. In afurther embodiment, the polymerizate can be transparent to that portionof the electromagnetic spectrum which activates the photochromicsubstance(s), i.e., that wavelength of ultraviolet (UV) light thatproduces the colored or open form of the photochromic substance and thatportion of the visible spectrum that includes the absorption maximumwavelength of the photochromic substance in its UV activated form, i.e.,the open form.

Photochromic compounds exhibit a reversible change in color when exposedto light radiation involving ultraviolet rays, such as the ultravioletradiation in sunlight or the light of a mercury lamp. Various classes ofphotochromic compounds have been synthesized and suggested for use inapplications in which a sunlight-induced reversible color change ordarkening is desired. The most widely described classes of photochromiccompounds are oxazines, pyrans and fulgides.

The general mechanism responsible for the reversible change in color,i.e., a change in the absorption spectrum in the visible range of light(400-700 nm), exhibited by different types of photochromic compounds hasbeen described and categorized. See John C. Crano, “ChromogenicMaterials (Photochromic)”, Kirk-Othmer Encyclopedia of ChemicalTechnology, Fourth Edition, 1993, pp. 321-332. The general mechanism forthe most common classes of photochromic compounds, e.g., indolinospiropyrans and indolino spirooxazines, involves an electrocyclicmechanism. When exposed to activating radiation, these compoundstransform from a colorless closed ring compound into a colored open ringspecies. In contrast, the colored form of fulgide photochromic compoundsis produced by an electrocyclic mechanism involving the transformationof a colorless open ring form into a colored closed ring form.

A wide variety of photochromic substances can be used in the presentinvention. In a non-limiting embodiment, organic photochromic compoundsor substances can be used. In alternate non-limiting embodiments, thephotochromic substance can be incorporated, e.g., dissolved, dispersedor diffused into the polymerizate, or applied as a coating thereto.

In a non-limiting embodiment, the organic photochromic substance canhave an activated absorption maximum within the visible range of greaterthan 590 nanometers. In a further non-limiting embodiment, the activatedabsorption maximum within the visible range can be range from at least590 to 700 nanometers. These materials can exhibit a blue, bluish-green,or bluish-purple color when exposed to ultraviolet light in anappropriate solvent or matrix. Non-limiting examples of such substancesthat are useful in the present invention include but are not limited tospiro(indoline)naphthoxazines and spiro(indoline)benzoxazines. These andother suitable photochromic substances are described in U.S. Pat. Nos.:3,562,172; 3,578,602; 4,215,010; 4,342,668; 5,405,958; 4,637,698;4,931,219; 4,816,584; 4,880,667; 4,818,096.

In another non-limiting embodiment, the organic photochromic substancescan have at least one absorption maximum within the visible rangeranging from 400 and less than 500 nanometers. In a further non-limitingembodiment, the substance can have two absorption maxima within thisvisible range. These materials can exhibit a yellow-orange color whenexposed to ultraviolet light in an appropriate solvent or matrix.Non-limiting examples of such materials can include certain chromenes,such as but not limited to benzopyrans and naphthopyrans. Many of suchchromenes are described in U.S. Pat. Nos. 3,567,605; 4,826,977;5,066,818; 4,826,977; 5,066,818; 5,466,398; 5,384,077; 5,238,931; and5,274,132.

In another non-limiting embodiment, the photochromic substance can havean absorption maximum within the visible range ranging from 400 to 500nanometers and an absorption maximum within the visible range rangingfrom 500 to 700 nanometers. These materials can exhibit color(s) rangingfrom yellow/brown to purple/gray when exposed to ultraviolet light in anappropriate solvent or matrix. Non-limiting examples of these substancescan include certain benzopyran compounds having substituents at the2-position of the pyran ring and a substituted or unsubstitutedheterocyclic ring, such as a benzothieno or benzofurano ring fused tothe benzene portion of the benzopyran. Further non-limiting examples ofsuch materials are disclosed in U.S. Pat. No. 5,429,774.

In some non-limiting embodiments, the photochromic substance for use inthe present invention can include photochromic organo-metaldithizonates, such as but not limited to (arylazo)-thioformicarylhydrazidates, such as but not limited to mercury dithizonates whichare described, for example, in U.S. Pat. No. 3,361,706. Fulgides andfulgimides, such as but not limited to 3-furyl and 3-thienyl fulgidesand fulgimides which are described in U.S. Pat. 4,931,220 at column 20,line 5 through column 21, line 38, can be used in the present invention.The relevant portions of the aforedescribed patents are incorporatedherein by reference.

In other non-limiting embodiments, the photochromic articles of thepresent invention can include one photochromic substance or a mixture ofmore than one photochromic substances. In other non-limitingembodiments, various mixtures of photochromic substances can be used toattain activated colors such as a near neutral gray or brown.

The amount of photochromic substance employed can vary. In somenon-limiting embodiments, the amount of photochromic substance and theratio of substances (for example, when mixtures are used) can be suchthat the polymerizate to which the substance is applied or in which itis incorporated exhibits a desired resultant color, e.g., asubstantially neutral color such as shades of gray or brown whenactivated with unfiltered sunlight, i.e., as near a neutral color aspossible given the colors of the activated photochromic substances. Insome non-limiting embodiments, the amount of photochromic substance usedcan depend upon the intensity of the color of the activated species andthe ultimate color desired.

In some non-limiting embodiments, the photochromic substance can beapplied to or incorporated into the polymerizate by various methodsknown in the art. In a non-limiting embodiment, the photochromicsubstance can be dissolved or dispersed within the polymerizate. In aother non-limiting embodiments, the photochromic substance can beimbibed into the polymerizate by methods known in the art. The term“imbibition” or “imbibe” includes permeation of the photochromicsubstance alone into the polymerizate, solvent assisted transferabsorption of the photochromic substance into a porous polymer, vaporphase transfer, and other such transfer mechanisms. In a non-limitingembodiment, the imbibing method can include coating the photochromicarticle with the photochromic substance; heating the surface of thephotochromic article; and removing the residual coating from the surfaceof the photochromic article. In alternate non-limiting embodiments, theimbibition process can include immersing the polymerizate in a hotsolution of the photochromic substance or by thermal transfer.

In some non-limiting embodiments, the photochromic substance can be aseparate layer between adjacent layers of the polymerizate, e.g., as apart of a polymer film; or the photochromic substance can be applied asa coating or as part of a coating placed on the surface of thepolymerizate.

The amount of photochromic substance or composition containing the sameapplied to or incorporated into the polymerizate can vary. In somenon-limiting embodiments, the amount can be such that a photochromiceffect discernible to the naked eye upon activation is produced. Such anamount can be described in general as a photochromic amount. In somenon-limiting embodiments, the amount used can depend upon the intensityof color desired upon irradiation thereof and the method used toincorporate or apply the photochromic substance. In general, the morephotochromic substance applied or incorporated, the greater the colorintensity. In some non-limiting embodiments, the amount of photochromicsubstance incorporated into or applied onto a photochromic opticalpolymerizate can be from 0.15 to 0.35 milligrams per square centimeterof surface to which the photochromic substance is incorporated orapplied.

In another embodiment, the photochromic substance can be added to thepolyurethane prior to polymerizing and/or cast curing the material. Inthis embodiment, the photochromic substance used can be chosen such thatit is resistant to potentially adverse interactions with, for example,the isocyanate present. Such adverse interactions can result indeactivation of the photochromic substance, for example, by trappingthem in either an open or closed form.

Further non-limiting examples of suitable photochromic substances foruse in the present invention can include photochromic pigments andorganic photochromic substances encapsulated in metal oxides such asthose disclosed in U.S. Pat. Nos. 4,166,043 and 4,367,170; organicphotochromic substances encapsulated in an organic polymerizate such asthose disclosed in U.S. Pat. No. 4,931,220.

The invention will be further described by reference to the followingexamples. Unless otherwise indicated, all parts and percentages are byweight.

EXAMPLES

The physical properties set forth below were measured as follows:

Light Transmittance (%) was measured according to ASTM E903-82;

Yellowness Index was measured according to ASTM D 1925-70;

Refractive index was measured on a multiple wavelength AbbeRefractometer Model DR-M2 manufactured by ATAGO Co., Ltd.; therefractive index of liquids were measured in accordance with ASTM-D1218; and the refractive index of solids were measured in accordancewith ASTM-D 542;

Density (grams/cm³) of solids was measured in accordance with ASTM-D792-00;

Taber Abrasion (% haze) was measured for up to 100 cycles using a TaberAbrader having a CS-10F abrasion wheel with 500 grams of weight, for asample size 3 inches by 3 inches by ⅛ inch (7.62 cm by 7.62 cm by 0.32cm) according to ASTM D 1044-99;

Bayer Abrasion (% haze) was measured for according to ASTM F 735-94(Reapproved 2001);

K-Factor crack propagation resistance was measured according to U.S.Dept. of Defense MIL-PRF-25690B (Jan. 29, 1993).

Tensile strength at yield, percent elongation at yield, and Young'sModulus were measured at about 25° C. in accordance with ASTM-D 638-03;

Gardner Impact Strength was measured in accordance with ASTM-D 5420-04;

Dynatup Multiaxial Impact Strength was measured in accordance withASTM-D 3763-02;

Shore D Hardness was measured in accordance with a Shore D durometer;

QUV-B testing was conducted for 1000 hours according to ASTM G-53;

Glass transition temperature (Tg) was measured using Dynamic MechanicalAnalysis; and

Linear Coefficient of Thermal Expansion was measured using a duPontThermomechanical analyzer (TMA) according to ASTM E 228-95.

The following abbreviations were used herein:

CHDM: 1,4-cyclohexane dimethanol;

Des N 3400: 60% hexamethylene diisocyanate dimer and 40% hexamethylenediisocyanate trimer commercially available from Bayer;

Des W: 4,4′-methylene-bis-(cyclohexyl isocyanate) commercially availablefrom Bayer;

MDI: Methylene diphenyl 4,4′-diisocyanate;

Polycaprolactone diol: Tone 0210 polycaprolactone diol having amolecular weight of 1000 g/mol commercially available from Solvay;

Polycarbonate diol 1: KM-10-1733 polycarbonate diol prepared fromhexanediol having a molecular weight of 1000 g/mol commerciallyavailable from Stahl;

Polycarbonate diol 2: KM10-1667 polycarbonate diol prepared fromhexanediol having a molecular weight of 1000 g/mol commerciallyavailable from Stahl;

TMDI: trimethylhexamethylene diisocyanate;

TMP: trimethylolpropane; and

TMXDI: meta-tetramethylxylylene diisocyanate.

Example A

Polyurethanes and poly(ureaurethane)s of Formulations 1 through 133 wereprepared from the components in amounts listed in Tables 1-18.

The polyurethanes (formulations not including water) were prepared in aglass kettle under nitrogen blanket with stirring. The polyisocyanatewas preheated to a temperature of about 100° C. before addition of theother components. The mixture was heated to a temperature of about 110°C. over about 10 minutes and maintained at this temperature for about 30minutes.

The poly(ureaurethane)s (formulations including water) also wereprepared in a glass kettle under nitrogen blanket with stirring. Thepolyisocyanate was preheated to a temperature of about 60° C.

For Formulations 123-127, 131, 132 and 133, the water was added to thepolyisocyanate and the temperature was maintained for about 30 minutesto form an isocyanate functional urea prepolymer. The other componentswere added and the mixture was heated to a temperature of about 90° C.over about 10 minutes and maintained at this temperature for about 30minutes.

For Formulations 128-130, about 0.15 equivalents of trimethylolpropanewas added to the polyisocyanate and the temperature was maintained forabout 120 minutes to form an isocyanate functional ureaurethaneprepolymer. The other components were added and the mixture was heatedto a temperature of about 11 0° C. over about 120 minutes and maintainedat this temperature for about 4 hours.

Each of the polyurethane and poly(ureaurethane) mixtures was degassed toremove carbon dioxide and cast into a 12″×13″×0.125″ (30.5 cm×33 cm×0.3cm) casting cell which had been preheated to a temperature of about 121°C. The filled cell was then cured in an oven for a period of about 48hours at about 121° C. TABLE 1 Branched Molecular Hard PolyisocyanatePolyol Diol Urethane Cyclic Weight per Segment Formulation Equiv- Equiv-Equiv- Content Content Crosslink Content No. Type alents Type alentsType alents (wt. %) (wt. %) (g/mole) (wt. %) 1 Des W 1.00 TMP 0.31,4-butanediol 0.7 33.49 45.98 1762 70.00 2 Des W 1.00 TMP 0.31,5-pentanediol 0.7 32.59 44.74 1810 71.00 3 Des W 1.00 TMP 0.61,5-pentanediol 0.4 32.99 45.29 1788 41.00 4 Des W 1.00 TMP 0.31,6-hexanediol 0.7 31.73 43.56 1860 71.00 5 Des W 1.00 TMP 0.3 Xyleneglycol 0.35 30.41 76.00 1940 71.00 CHDM 0.35 6 Des W 1.00 TMP 0.31,5-pentanediol 0.35 31.37 58.00 1881 72.00 CHDM 0.35 7 Des W 1.00 TMP0.3 1,6-hexanediol 0.35 30.97 57.34 1905 72.00 CHDM 0.35 8 Des W 1.00TMP 0.3 1,8-octanediol 0.7 30.14 41.37 1958 73.00 9 Des W 1.00 TMP 0.31,10-decanediol 0.7 28.70 39.40 2056 74.00 10 Des W 1.00 TMP 0.31,8-octanediol 0.35 29.40 40.36 2007 74.00 1,10-decanediol 0.35 11 Des W1.00 TMP 0.8 CHDM 0.2 32.53 53.60 1814 22.00 12 Des W 1.00 TMP 0.3 CHDM0.7 30.24 70.50 1951 73.00 13 Des W 1.00 TMP 0.8 1,5-pentanediol 0.233.26 45.67 1774 21.00 14 Des W 1.00 TMP 0.3 1,7-heptanediol 0.7 30.9142.44 1909 72.00 15 Des 1.00 TMP 0.3 1,9-nonanediol 0.7 29.40 40.36 200773.00 16 Des W 1.00 TMP 0.3 1,12-dodecanediol 0.7 27.39 37.60 2154 75.6017 Des W 1.00 TMP 0.6 1,10-decanediol 0.4 30.59 42.00 1929 45.00 18 DesW 1.00 TMP 0.4 1,10-decanediol 0.4 29.75 40.84 1983 45.00 CHDM 0.2 19Des W 1.00 TMP 0.3 1,10-decanediol 0.65 26.52 36.40 2225 63.00Polycarbonate diol 1 0.05 20 TMDI 1.00 TMP 0.3 CHDM 0.7 34.91 47.92 169073.00

TABLE 2 Branched Molecular Hard Polyisocyanate Polyol Diol UrethaneCyclic Weight per Segment Formulation Equiv- Equiv- Equiv- ContentContent Crosslink Content No. Type alents Type alents Type alents (wt.%) (wt. %) (g/mole) (wt. %) 21 Des W 1.00 TMP 0.3 1,4-butanediol 0.627.54 37.81 2142 49.00 Polycarbonate diol 1 0.1 22 Des W 1.00 TMP 0.3Isopropylidene 0.7 25.79 35.41 2287 77.00 dicyclohexanol 23 Des W 1.00TMP 0.4 1,10-decanediol 0.5 25.08 34.44 2352 46.00 Polycarbonate diol 10.1 24 Des W 1.00 TMP 0.3 1,10-decanediol 0.6 24.64 33.83 2395 46.00Polycarbonate diol 1 0.1 25 Des W 1.00 TMP 0.3 1,4-butanediol 0.5 23.3832.10 2523 54.00 Polycarbonate diol 1 0.2 26 Des W 1.00 TMP 0.41,10-decanediol 0.6 29.30 40.23 2013 65.00 27 Des W 0.5 TMP 0.31,10-decanediol 0.7 29.13 39.99 2025 MDI 0.5 28 Des W 1.00 TMP 0.3 1,12-0.7 27.48 37.72 2147 cyclododecanediol 29 TMDI 1.00 TMP 0.2 CHDM 0.834.35 47.16 1718 73.00 30 1.00 TMP 0.3 Decanediol 0.45 29.34 40.28 2011Xylene Glycol 0.25 31 Des W 0.3 TMP 0.3 1,10-decanediol 0.7 31.50 43.241873 TMDI 0.7 32 Des W 0.8 TMP 0.3 1,10-decanediol 0.5 27.62 37.92 213675.00 Bis(2-hydroxyethyl) 0.2 terephthalate 34 Des W 0.75 TMP 0.31,10-decanediol 0.7 28.91 39.69 2041 MDI 0.25

TABLE 3 Branched Molecular Hard Polyisocyanate Polyol Diol UrethaneCyclic Weight per Segment Formulation Equiv- Equiv- Equiv- ContentContent Crosslink Content No. Type alents Type alents Type alents (wt.%) (wt. %) (g/mole) (wt. %) 35 Des W 0.85 TMP 0.3 1,10-decanediol 0.728.83 39.58 2047 MDI 0.15 36 TMXDI 1.00 TMP 0.3 1,4-butanediol 0.7 35.3148.47 1671 37 Des W 1.00 TMP 0.3 1,10-decanediol 0.6 28.91 39.69 204175.00 1,4-cyclohexane 0.1 dimethanol 38 Des W 1.00 TMP 0.31,10-decanediol 0.6 28.24 38.78 2089 74.00 Isopropylidene 0.10Dicyclohexanol 39 Des W 1.00 TMP 0.3 1,8-octanediol 0.45 29.61 40.651993 70.00 1,10-decanediol 0.25 40 Des W 1.00 TMP 0.35 1,10-decanediol0.65 29.00 39.81 2035 74.00 41 Des W 1.00 TMP 0.3 1,8-octanediol 0.429.50 40.50 2000 1,10-decanediol 0.30 42 Des W 1.00 TMP 0.31,8-octanediol 0.5 29.71 40.79 1986 73.00 1,10-decanediol 0.20 43 Des W1.00 TMP 0.3 1,4-butanediol 0.1 28.12 38.61 2098 75.00 1,12-dodecanediol0.60 44 Des W 1.00 TMP 0.3 1,10-decanediol 0.35 26.60 36.52 2218 76.00Isopropylidene 0.35 dicyclohexanol 45 Des N 3400 1.00 1,10-decanediol 1.20.93 28.73 2820 46 Des N 3400 1.00 1,10-decanediol 0.8 21.15 29.04 2790CHDM 0.20 47 Prepolymer 1.00 1,4-butanediol 0.75 13.29 18.24 4441 CHDM0.25

TABLE 4 Branched Molecular Hard Polyisocyanate Polyol Diol UrethaneCyclic Weight per Segment Formulation Equiv- Equiv- Equiv- ContentContent Crosslink Content No. Type alents Type alents Type alents (wt.%) (wt. %) (g/mole) (wt. %) 48 Des W 1.00 TMP 0.3 1,4-butanediol 0.3533.04 45.35 1786 70.00 1,5-pentanediol 0.35 49 Des W 1.00 TMP 0.31,5-pentanediol 0.6 32.22 44.23 1831 71.00 1,8-octanediol 0.10 50 Des W1.00 TMP 0.3 1,5-pentanediol 0.6 31.97 43.89 1845 71.00 1,10-decanediol0.10 51 Des W 1.00 TMP 0.3 1,4-butanediol 0.2 32.84 45.09 1796 71.001,5-pentanediol 0.50 52 Des W 1.00 TMP 0.3 1,4-butanediol 0.5 33.2345.62 1775 70.00 1,5-pentanediol 0.20 53 Des W 1.00 TMP 0.31,4-butanediol 0.6 32.99 45.29 1789 70.00 CHDM 0.10 54 Des W 1.00 TMP0.3 1,5-pentanediol 0.6 32.23 44.25 1830 71.00 CHDM 0.10 55 Des W 1.00TMP 0.3 1,5-pentanediol 0.5 31.88 43.77 1850 71.00 CHDM 0.20 56 Des W1.00 TMP 0.3 1,5-pentanediol 0.5 30.09 41.32 1960 71.00Bis(2-hydroxyethyl) 0.20 terephthalate 57 Des W 1.00 TMP 0.31,5-pentanediol 0.6 31.19 42.82 1892 73.00 Isopropylidene 0.10dicyclohexanol 58 Des W 1.00 TMP 0.3 1,5-pentanediol 0.5 22.99 31.562566 35.00 Polycarbonate diol 1 0.2 59 Des W 1.00 TMP 0.31,5-pentanediol 0.6 26.96 37.01 2188 50.00 Polycarbonate diol 1 0.1 60Des W 1.00 TMP 0.3 1,5-pentanediol 0.3 26.25 36.04 2247 64.00 CHDM 0.3Polycarbonate diol 1 0.10 61 Des W 1.00 TMP 0.4 1,5-pentanediol 0.122.55 30.95 2617 37.00 CHDM 0.3 Polycarbonate diol 1 0.20

TABLE 5 Branched Molecular Hard Polyisocyanate Polyol Diol UrethaneCyclic Weight per Segment Formulation Equiv- Equiv- Equiv- ContentContent Crosslink Content No. Type alents Type alents Type alents (wt.%) (wt. %) (g/mole) (wt. %) 62 Des W 1.00 TMP 1.0 Polycarbonate diol 10.05 30.24 41.52 616 0.00 63 Des W 1.00 TMP 1.0 Polycarbonate diol 10.25 31.81 43.67 560 0.00 64 Des W 1.00 TMP 0.9 Polycarbonate diol 1 0.127.53 37.80 716 0.00 65 Des W 1.00 TMP 1.0 Polycarbonate diol 1 0.0132.82 45.06 543 0.00 66 Des W 1.00 TMP 1.00 33.54 46.05 1759 0.00 67 DesW 1.00 TMP 0.35 1,5-pentanediol 0.65 32.66 44.83 1562 66.00 68 Des W1.00 TMP 0.40 1,5-pentanediol 0.6 32.72 44.93 1363 61.00 69 Des W 1.00TMP 0.70 1,5-pentanediol 0.3 33.13 45.48 770 31.00 70 Des W 1.00 TMP0.65 1,5-pentanediol 0.35 33.06 45.39 1785 36.00 71 Des W 1.00 TMP 0.551,5-pentanediol 0.45 32.92 45.20 1792 46.00 72 Des W 1.00 TMP 0.501,5-pentanediol 0.5 32.86 45.11 1796 51.00 73 Des W 1.00 TMP 0.451,5-pentanediol 0.55 32.79 45.02 1799 56.00 74 Des W 1.00 TMP 0.701,10-decanediol 0.3 31.28 42.94 1886 35.00 75 Des W 1.00 TMP 0.651,10-decanediol 0.35 30.93 42.47 1907 76 Des W 1.00 TMP 0.551,10-decanediol 0.45 30.26 41.54 1950 51.00 77 Des W 1.00 TMP 0.501,10-decanediol 0.5 29.93 41.10 1971 55.00 78 Des W 1.00 TMP 0.451,10-decanediol 0.55 30.26 41.54 1950 79 Des W 1.00 TMP 0.251,10-decanediol 0.75 28.41 39.00 2077 79.00 80 Des W 1.00 TMP 0.201,10-decanediol 0.8 28.12 38.60 2098 83.00 81 Des W 1.00 TMP 0.151,10-decanediol 0.85 27.84 38.22 2119 88.00 82 Des W 1.00 TMP 0.101,10-decanediol 0.9 27.56 37.84 2141 61.00 83 Prepolymer 1.001,4-butanediol 1.00 20.12 27.62 2933 84 Prepolymer 1.00 1,4-butanediol0.75 19.66 27.00 3001 CHDM 0.25 85 Des W 0.41 PEG 0.03 1,4-butanediol0.3565 56.78 77.95 1039 Polycaprolactone diol 0.003 Pluronic 0.03 86 DesW 1.00 TMP 0.30 1,5-pentanediol 0.46 21.71 29.80 2718 31.00Polycarbonate diol 1 0.24 87 Des W 1.00 TMP 0.30 1,5-pentanediol 0.4722.02 30.22 2680 Polycarbonate diol 1 0.23 88 Des W 1.00 TMP 0.301,5-pentanediol 0.48 22.33 30.66 2642 Polycarbonate diol 1 0.22

TABLE 6 Branched Molecular Hard Polyisocyanate Polyol Diol UrethaneCyclic Wt. per Segmt Formulation Equiv- Equiv- Equiv- Content ContentCrosslink Content No. Type alents Type alents Type alents (wt. %) (wt.%) (g/mole) (wt. %) 89 Des W 1.00 TMP 0.30 1,5-pentanediol 0.49 22.6531.10 2604 Polycarbonate diol 1 0.21 90 Des W 1.00 TMP 0.301,5-pentanediol 0.51 23.33 32.03 2529 Polycarbonate diol 1 0.19 91 Des W1.00 TMP 0.30 1,5-pentanediol 0.52 23.69 32.52 2491 Polycarbonate diol 10.18 92 Des W 1.00 TMP 0.30 1,5-pentanediol 0.53 24.05 33.02 2453Polycarbonate diol 1 0.17 93 Des W 1.00 TMP 0.30 1,5-pentanediol 0.5424.43 33.54 2415 Polycarbonate diol 1 0.16 94 Des W 1.00 TMP 0.301,5-pentanediol 0.55 24.82 34.07 2377 42.00 Polycarbonate diol 1 0.15 95Des W 1.00 TMP 0.3 1,5-pentanediol 0.5 22.80 31.30 2020 Polycarbonatediol 2 0.2 96 Des W 1.00 TMP 0.3 1,5-pentanediol 0.65 29.43 40.41 200559.00 Polycarbonate diol 2 0.05 97 Des W 1.00 TMP 0.3 1,4-butanediol0.65 30.11 41.34 1959 Polycarbonate diol 2 0.05 98 Des W 1.00 TMP 0.31,5-pentanediol 0.6 26.83 36.84 2199 Polycarbonate diol 2 0.1 99 Des W1.00 TMP 0.3 1,4-butanediol 0.5 23.31 32.00 2532 Polycarbonate diol 10.2 100 Des W 1.00 TMP 0.3 1,4-butanediol 0.6 27.49 37.73 2147Polycarbonate diol 1 0.1 101 Des W 1.00 TMP 0.30 1,4-butanediol 0.4621.97 30.16 2686 Polycarbonate diol 1 0.24 102 Des W 1.00 TMP 0.301,4-butanediol 0.47 22.29 30.60 2647 Polycarbonate diol 1 0.23 103 Des W1.00 TMP 0.30 1,4-butanediol 0.48 22.62 31.05 2609 Polycarbonate diol 10.22 104 Des W 1.00 TMP 0.30 1,4-butanediol 0.49 22.96 31.52 2570Polycarbonate diol 1 0.21 105 Des W 1.00 TMP 0.30 1,4-butanediol 0.5123.67 32.49 2493 Polycarbonate diol 1 0.19

TABLE 7 Branched Molecular Hard Polyisocyanate Polyol Diol UrethaneCyclic Weight per Segment Formulation Equiv- Equiv- Equiv-  ContentContent  Crosslink  Content No. Type alents Type alents Type alents (wt.%) (wt. %) (g/mole) (wt. %) 106 Des W 1.00 TMP 0.30 1,4-butanediol 0.5224.04 33.00 2455 Polycarbonate diol 1 0.18 107 Des W 1.00 TMP 0.301,4-butanediol 0.53 24.42 33.52 2416 Polycarbonate diol 1 0.17 108 Des W1.00 TMP 0.30 1,4-butanediol 0.54 24.81 34.07 2378 Polycarbonate diol 10.16 109 Des W 1.00 TMP 0.30 1,4-butanediol 0.55 25.22 34.63 2339Polycarbonate diol 1 0.15 110 Des W 1.00 TMP 0.05 CHDM 0.95 29.22 40.112019 111 Des W 1.00 TMP 0.05 Isopropylidene bis 0.95 13.43 18.44 1290096.00 [(2-(2,6-dibromo- phenoxy)ethanol 112 Des W 1.00 TMP 0.05 CHDM 0.529.42 40.38 2006 96.00 Xylene glycol 0.45 113 Des W 1.00 TMP 0.051,8-octanediol 0.95 29.08 39.92 2029 114 Des W 1.00 TMP 0.051,10-decanediol 0.95 27.29 37.47 2162 115 Des W 1.00 TMP 0.05 CHDM 0.9526.69 36.64 10965 Polycarbonate diol 1 0.05 116 Des W 1.00 TMP 0.051,4-butanediol 0.95 33.48 78.00 10570 95.00 117 Des W 1.00 TMP 0.051,5-pentanediol 0.95 32.26 44.30 11000 96.00 118 Des W 1.00 TMP 0.30Polycaprolactone diol 0.2 23.31 32.00 2531 1,5-pentanediol 0.5 119 Des W1.00 TMP 0.30 Polycaprolactone diol 0.15 25.10 34.46 23511,5-pentanediol 0.55 120 Des W 1.00 TMP 0.30 Dibutyl-1,3- 0.7 28.0338.48 2105 75.00 propanediol 121 Des W 1.00 TMP 0.30 Neopentyl glycol0.7 32.58 44.74 1811 71.00 122 Des W 1.00 TMP 0.30 Ethylene glycol 0.735.50 48.80 1661 70.00

TABLE 8 Formulation Light Yellowness Refractive Density No.Transmittance (%) Index Index (g/cm³) 1 91.84 0.44 1.524 1.1417 2 91.910.34 1.531 1.1307 3 91.9 0.33 1.531 1.1388 4 91.88 0.4 1.531 1.1209 591.58 0.66 1.544 1.1346 6 91.84 0.37 1.533 1.1261 7 91.87 0.34 1.5311.1144 8 91.8 1.65 1.524 1.1051 9 91.93 0.5 1.527 1.0912 10 91.72 1.71.527 1.0929 15 1.524 1.0969 16 1.52 1.0685 17 1.525 1.1002 18 1.5171.0976 19 1.521 1.0886 20 1.517 1.0979 21 1.517 1.1327 23 1.523 1.104324 1.517 1.0971 25 1.521 1.1372 26 1.525 1.0876 29 1.512 1.0984 30 1.5311.1049 31 1.508 1.072 32 1.527 1.1123 37 1.522 1.086 38 1.522 1.0831 391.524 1.0921 40 1.525 1.0846 41 1.522 1.0866 42 1.524 1.0928 43 1.5251.076 44 1.526 1.0796 58 1.145

TABLE 9 Tensile Gardner Taber Abrasion Bayer Modulus at ElongationImpact Formulation # % Abrasion % Yield at Yield Strength No. CyclesHaze Haze K-Factor (lb/in²) (%) (In-lbs) 1 100 28.5 29.45 1245.6 33600041 427 2  60+ 30.8 31.48 1362.4 367000  19/38 628 3 100 20.5 22.55781.83 350000 3.9/19 100 4 100 29 35.87 1313.6 311000 56 595 5 100 27.826.53 902.82 338000 4.7 168 6 100 24.7 28.75 1152.1 339000 32 214 7 10028.6 33.05 1230.1 327000 34 236 8 100+ 31.1 39.92 1522.3 287000 55 584 9100+ 32.4 47.7 3564.8 251000 14 576 10 100+ 31 44.75 3104.1 258000 17593 15  60+ 32.7 42.17 2073 259000 16 512 16  60 45.9 45.5 3621 23800019 365 17 100 28.7 32.7 940 295000 8.4 158 18 26.4 34.68 1227 286000 14220 19 33.9 45.9 4309 260000 14 595 20 25.1 42.88 1765 378000 4.3 553 2128 40.77 3211 312000 14 536 23 38 43.08 4628 265000 12 461 24 39.1 43.174869 251000 15 497 25 24.5 37.83 4528 246000 14 627 26 38.1 38.78 1415262000 19 179 28 42.6 834 327000 3 29 40.4 33.88 2351 369000 4.4 146 3022.4 38.78 1150 274000 16 204 31 41.8 25.32 2252 216000 433 32 41.8346.55 1852 278000 14 518

TABLE 10 Tensile Gardner Taber Abrasion Bayer Modulus at ElongationImpact Formulation # % Abrasion % Yield at Yield Strength No. CyclesHaze Haze K-Factor (lb/in²) (%) (In-lbs) 38 45.82 41.72 1319 264000 15614 39 46.58 38.47 1749 256000 18 632 40 45.78 44.52 1651 255000 22 53141 45.02 41.7 1771 247000 16 356 42 36.23 41.12 1777 249000 18 581 4343.12 40.85 4005 238000 15 598 44 41.88 35.67 997 279000 4.6 71 48295000 5.4 192 49 295000 6.1 327 50 284000 8.6 104 51 290000 5.6 426 52294000 8.3 71 53 299000 5.3 112 54 292000 5.3 111 55 292000 5.9 164 56314000 5.7 40 57 299000 5.1 70 58 215000 20 365 59 4035 283000 10 299 601598 284000 18 379 61 260000 17 546 62 876 346000 3.2 24 63 737 3340004.2 14 64 1119 349000 2.9 27 65 669 357000 2.8 66 638 368000 2.4 12 67216

TABLE 11 Taber Abrasion Bayer Tensile Elongation Gardner ImpactFormulation # % Abrasion % Modulus at at Yield Strength No. Cycles HazeHaze K-Factor Yield (lb/in²) (%) (In-lbs) 68 203 69 133 70 80 71 56 72106 73 136 74 40 75 38 76 63 77 64 78 125 79 333 80 376 81 376 82 346 832235 84 2185 86 317 87 328 88 451 89 227000 15 472 90 244000 11 445 91255000 21 411 92 263000 19 426 93 266000 9 443 94 270000 12 403 95259000 13 406 96 280000 19 255 97 299000 5 290 98 272000 13 405 99 346100 333 101 363 102 364

TABLE 12 Tensile Gardner Bayer Modulus at Elongation Impact FormulationTaber Abrasion Abrasion % Yield at Yield Strength No. # Cycles % HazeHaze K-Factor (lb/in²) (%) (In-lbs) 103 367 104 367 105 360 106 404 107362 108 371 109 327 110 97 113 334 114 552 118 82

TABLE 13 Coefficient Dynatup Glass of Thermal Formulation Impact Shore DTransition Expansion No. Strength Hardness Temp. (in/in) 1 17.6 79 126 224.28 88 119 81.91 3 4.04 88 140 4 25.4 86 117.1 5 8.6 88 156 6 15.2 86132 7 27.2 86 129.9 8 31.5 82 106 9 38.4 80 99.1 94.65 10 35.5 81 102 1524.8 80 105 16 34.4 79 93 17 13.9 88 123.9 18 40.9 83 119 19 44.3 8189.1 20 26.1 83 75.1 70.01 21 39.6 81 97 23 17.9 79 87 101.11 24 33.4 8079.2 97.2 25 44.9 78 76.1 95.66 26 28.6 84 106 29 5.34 85 71.1 72.36 3030.7 85 120.1 31 41 79 52.1 96.91 32 46.5 82 104 38 33.2 81 111.1 3932.9 81 103.9 40 41.9 81 101.1 41 27.5 80 42 25.1 81 43 35.3 80 97 443.15 86 48 25.2 49 4.24 50 26.3 51 21.6 52 31.6 53 22.2 54 26.7 55 41.656 20.7

TABLE 14 Coefficient Dynatup Glass of Thermal Formulation Impact Shore DTransition Expansion No. Strength Hardness Temp. (in/in) 57 17.2 58 62.366 59 36.6 60 37.4 61 38.9 62 152 63 134 64 150 65 174 66 166 67 161 8942.6 90 48.4 91 50.2 92 48 93 56.5 94 45.1 95 47.5 96 47.5 97 34.3 9839.2

TABLE 15 Molecular Weight Hard Urethane Cyclic per Segment FormulationPolyisocyanate Branched Polyol Diol Content Content Crosslink ContentWater No. Type Equivalents Type Equivalents Type Equivalents (wt. %)(wt. %) (g/mole) (wt. %) (Equivalents) 123 Des W 1.00 TMP 0.31,5-pentanediol 0.554 29.67 40.74 1988 0.19 Polycarbonate 0.57 diol 1124 Des W 1.00 TMP 0.3 1,5-pentanediol 0.374 27.73 38.07 2128 0.22Polycarbonate 0.11 diol 1 125 Des W 1.00 TMP 0.3 1,5-pentanediol 0.534.22 46.98 1724 0.20 126 Des W 1.00 TMP 0.3 1,5-pentanediol 0.45 30.8542.35 1913 0.20 Polycarbonate 0.05 diol 1 127 Des W 1.00 TMP 0.31,5-pentanediol 0.4 28.08 38.55 2101 0.20 Polycarbonate 0.1 diol 1 128Des W 1.00 TMP 0.30 CHDM 0.6 31.25 42.91 1888 0.1 129 Des W 1.00 TMP0.90 34.24 47.00 1723 0.1 130 Des W 1.00 TMP 0.30 CHDM 0.55 31.79 43.641856 0.15 131 Des W 1.00 TMP 0.3 1,5-pentanediol 0.55 30.17 41.42 19560.10 Polycarbonate 0.05 diol 1 132 Des W 1.00 TMP 0.3 1,5-pentanediol0.5 27.52 37.78 2144 0.10 Polycarbonate 0.1 diol 1 133 Des W 1.00 TMP0.3 1,5-pentanediol 0.55 33.80 46.40 1746 0.15

TABLE 16 Formulation Light Transmittance Yellow Refractive Density No.(%) Index Index (g/cm³) 125 1.119 126 1.125 127 1.133 128 1.113 1291.128 130 1.113 131 1.127 132 1.129

TABLE 17 Tensile Gardner Bayer Modulus at Elongation Impact FormulationTaber Abrasion Abrasion Yield at Yield Strength No. # Cycles % Haze %Haze K-Factor (lb/in²) (%) (In-lbs) 125 355000 13 51 126 1113 305000 424 127 1551 282000 12 244 128 853 369000 16 56 129 686 441000 7.5 8 130766 389000 15 37 131 290000 7.7 126 132 289000 19 328 133 289000 11 224

TABLE 18 Coefficient Dynatup Glass of Thermal Formulation Impact Shore DTransition Expansion No. Strength Hardness Temp. (in/in) 125 137 12614.6 115 127 30 67 128 3.31 161 129 3 130 8.67 153 131 32.5 132 133 9.29

The above samples exhibited low yellowness, high light transmittance,high impact strength and good ballistic resistance.

A 6″×6″ (15.2 cm×15.2 cm) laminate of 2 inches (5.1 cm) of moldedFormulation 2 below facing outward, laminated to a 1″ (2.5 cm) ply ofmolded Formulation 9 below, and 0.5″ (1.3 cm) of molded Formulation 60stopped or deflected four consecutive AK-47, 7.62 mm×39 mm shots from150 feet (45.7 m). Each layer was molded as described above. No glassply was used in the laminate. The laminate was heated in an autoclave atabout 300° F. (149° C.) for about 2 hours.

Samples of Polycast 84 aerospace stretched acrylic (commerciallyavailable from Spartech of Clayton, Mo.) and samples of polymer ofExample A, Formulation 2 (synthesized at 110° C. and cured at 143° C. asdiscussed above) were evaluated for physical properties as set forth inTable 19 below. The Sample of Example A, Formulation 2 had lowerdensity, higher impact strength and elongation, and was tougher than thetested sample of stretched acrylic. LEXAN #8574K26 polycarbonate(commercially available from McMaster Carr Supply Co. of Cleveland,Ohio) and samples of polymer of Example A, Formulation 84 (synthesizedat 110° C. and cured at 143° C. as discussed above) were evaluated forphysical properties as set forth in Table 20 below. The Example A,Formulation 84 had better solvent resistance, UV resistance and higherimpact strength than the tested sample of LEXAN. TABLE 19 Sample ofFormulation 2 Property Stretched Acrylic of Example A Light Transmission92 92 % Haze <1% <0.1% Density 1.18 1.13 Solvent/75% aqueous sulfuric1000-4000 psi stress acid resistance K factor 2400 1500 Gardner ImpactTest (in-lbs) 16 628 High Speed Multiaxial Impact 3.6 (unprocessed) 26.5% Elongation (at break) <5 38% % Elongation (1000 hrs <5 40% QUV-B)Tensile Strength 11,250 11,800 Tensile Modulus 450,000 367,000 GlassTransition Temperature 205 247° F. (119° C.) Heat Distortion Temp.shrinks above 180° F. 235° F. (113° C.) Abrasion Resistance: % Haze, 3015 100 cycles Taber Abrader Refractive Index 1.49 1.519 Shore DDurometer 94 90

TABLE 20 Sample of Formulation 84 Property Polycarbonate of Example ALight Transmission 88 92 Density 1.2 1.08 Solvent Resistance Poor OH,H+, Good OH, H+, Acetone Acetone Gardner Impact Mean Failure 588in-lb >640 in-lbs Energy (>72 J) High Speed Multiaxial Impact 72 joules105 Joules % Haze, 100 cycles Taber Abrader 60% 15% Refractive Index1.586 1.519 Tensile Modulus 320,000 300,000 Tensile Strength 8000 psi8500 psi % Elongation (at break) 100%  200%  % Elongation (1000 hrsQUV-B) severe degradation 97% brittle-yellow Heat Distortion Temp. 275°F. 220° F. Glass Transition Temperature 305 F. 240 F. Shore D Durometer85 80DMA Testing

A sample of Formulation 114 (prepared from 0.95 equivalents of1,10-decanediol, 0.05 equivalents of trimethylolpropane and 1.0equivalents of 4,4′-methylene-bis-(cyclohexyl isocyanate) (DESMODUR W))using Dynamic Mechanical Analysis (DMA) for storage modulus, lossmodulus and tan delta. The DMA analysis was conducted on a solid,clamped sample (2″×2″×⅛″) (5.1 cm×5.1 cm×0.3 cm) vibrated at a frequencyof 1 Hz over a wide temperature range increased at a rate of 3° C./min.As shown in FIG. 16, the sample exhibited a low temperature transitionin the loss modulus at about −70° C., which is unusual for glasspolymers and indicates molecular torsional motion at this lowtemperature. A second transition is present at about 14° C. The glasstransition temperature of this polymer is 71° C., which is a maximum inthe tan delta graph. At this temperature, the polymer is most efficientat converting mechanical vibrations into heat, thus it is at thistemperature that the polymer reaches a maximum in damping properties.The storage modulus is the energy conserved by the polymer and can berelated to the Young's Modulus or stiffness of the polymer.

Ballistics Testing

Example AA

A 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) thick sample of Formulation 2 fromExample A above was cured at by heating at 290° F. (143° C.) for 48hours. Four 0.40 caliber bullets shot from 30 feet (9.1 m) at a velocityof 987 ft/sec (300 m/sec) ricocheted off the surface of the sample andthe plastic did not crack. A photograph of a perspective view of thetest sample is shown in FIG. 17.

Example AB

A 6″×6″×⅜″ (15.2 cm×15.2 cm×1 cm) formulation thick sample ofFormulation 2 from Example A above was cured at by heating at 290° F.(143° C.) for 48 hours. A 12 gauge shotgun shot from 20 feet (6.1 m) ata velocity of 1290 ft/sec (393 m/sec) using heavy game lead shot pelletsricocheted off the surface of the sample and the plastic did not crack.A photograph of a front elevational view of the test sample is shown inFIG. 18.

Example AC

A 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) thick sample of Formulation 93 fromExample A above was cured at by heating at 290° F. (143° C.) for 48hours. Three 9 mm bullets shot from 20 feet (6.1 m) at a velocity of1350 ft/sec (411 m/sec) stuck in the sample. A photograph of a frontelevational view of the test sample is shown in FIG. 19.

Example AD

A 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) thick sample of Formulation 94 fromExample A above was cured at by heating at 290° F. (143° C.) for 48hours. A 9 mm bullet shot from 20 feet (6.1 m) at am initial velocity of1350 ft/sec (411 m/sec) stuck in the sample. Photographs of the testsample is shown in FIGS. 20 and 21. FIG. 20 is a perspective view of thesample showing the bullet embedded in the sample surface. FIG. 21 is aside elevational view of the sample showing the bullet entrance into thesample.

Example AE

A 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) thick sample of Formulation 2 fromExample A above was cured at by heating at 290° F. (143° C.) for 48hours. A 6″×6″×1″ thick sample of Formulation 9 from Example A above wascured at by heating at 290° F. (143° C.) for 48 hours. A 6″×6″×0.5″(15.2 cm×15.2 cm×1.75 cm) thick sample of Formulation 58 from Example Aabove was cured at by heating at 290° F. (143° C.) for 48 hours. Acomposite was prepared by assembling a 1″ (2.5 cm) thick layer of thesample of Formulation 2, a 1″ (2.5 cm) thick layer of the sample ofFormulation 9, and a 0.5″ (1.25 cm) thick layer of the sample ofFormulation 58 such that the layer of Formulation 2 faced the rifle.

Four 7.62×39 mm bullets having a steel core were shot from an AK-47rifle from a distance of 30 yards (27.4 m) at an initial velocity of2700 ft/sec (823 m/sec). The first bullet stopped in the middle layer ofFormulation 9, generally parallel to the initial shot direction. Thesecond through fourth bullets stopped in the far layer of Formulation58, generally parallel to the initial shot direction. Photographs of thetest sample is shown in FIGS. 22 and 23. FIG. 22 is a front elevationalview of a portion of the sample showing bullet entry points and twobullets embedded in the sample surface. FIG. 23 is a rear perspectiveview of the sample showing the two exiting bullets lodged in theFormulation 58 layer of the sample.

Example AF

Samples prepared from Formulations 58 and 89-97 of Example A aboveperformed similarly, i.e., all “caught” bullets. A sample prepared fromFormulation 94 showed the least amount of sample penetration with about⅛″ of the back of the bullet protruding from the surface. No ductilebulge was observed in the back of sample prepared from Formulation 94.Penetration was greatly reduced compared to samples prepared fromFormulations 58 and 89-92

Example B

Comparative Non-limiting Example of Processing Temperature of 80° C. vs.110° C.

Short chain diols (aliphatic diols having 4 to 8 carbon atoms asdiscussed above) are typically immiscible in isocyanates due to thepolarity difference and surface tension difference between the twomaterials. It has been found that when the short chain diol andisocyanate are mixed at 80° C. or less, they take longer to become aclear solution than at 110° C. or higher. Although the solutions mayboth appear clear, it has been found that there is an inhomogeneity thatmanifests itself in cured articles as much lower impact strengths thanwhen the solutions are made at or above 110° C. In addition, whencasting or reaction injection molding into a glass mold, any coolingthat occurs from pouring and exposure to air, or the mold temperaturebeing below 100° C. exacerbates the inhomogeneity problem as furthercooling increases the inhomegeneity. If temperatures drop even further,the short chain diol and isocyanate will phase separate and appear ashaze. This haze generally will not clear in an oven heated to 120° C. to140° C. after pouring into a mold and heating for 24 to 48 hours. Highervariations in impact strength also have been observed as the processingtemperatures drop below 100° C. Above 110° C., the initial Gardnerimpact strengths for polymers of this invention are higher initially,and show less variation in impact strengths from batch to batch whenprocessed above 110° C. The examples below illustrate the temperatureeffect.

Example B1

The following components 20.1 grams of 1,5 pentanediol, 7.5 grams oftrimethylolpropane and 72.45 grams of DESMODUR W containing 20%trans-trans isomer of 4,4′-methylene-bis-(cyclohexyl isocyanate) werecharged into a glass kettle fitted with a thermometer and overheadstirrer. The charge was brought up to a temperature of 110° C. to 120°C. while mixing and applying vacuum (2 mm mercury (266 Pa)) to removebubbles. The batch was mixed for 10 to 20 minutes after reaching 110° C.to 120° C.

The batch was cast into a heated glass mold that was preheated in anoven at 140° C. The polymer was cured for 48 hours at 140° C. withoutcatalyst. After curing, the mold was removed from the oven and allowedto cool to room temperature. The plastic sheet was then removed from theglass mold and cut into 2″×2″×⅛″ (5.1 cm×5.1 cm×0.3 cm) samples forGardner Impact testing. The initial Gardner impact strength averaged 260in-lbs (30 J).

Example B2

The following components 20.1 grams of 1,5 pentanediol, 7.5 grams oftrimethylolpropane and 72.45 grams of DESMODUR W containing 20%trans-trans isomer of 4,4′-methylene-bis-(cyclohexyl isocyanate) werecharged into a glass kettle fitted with a thermometer and overheadstirrer. The charge was brought up to a temperature of 80° C. to 90° C.while mixing and applying vacuum (2 mm mercury (266 Pa)) to removebubbles. The batch was mixed for 1 to 2 hours after reaching 80° C. to90° C. until the batch appeared clear.

The batch was cast into a heated glass mold that has been preheated inan oven at 140° C. The polymer was cured for 48 hours at 140° C. withoutcatalyst. After curing, the mold was removed from the oven and allowedto cool to room temperature. The plastic sheet was removed from theglass mold and cut into 2″×2″×⅛″ (5.1 cm×5.1 cm×0.3 cm) samples forGardner Impact testing. The initial Gardner impact strength averaged 62in-lbs (7 J).

Example B3

The following components 17.9 grams of 1,4 butanediol, 7.4 grams oftrimethylolpropane and 74.47 grams of DESMODUR W containing 20%trans-trans isomer of 4,4′-methylene-bis-(cyclohexyl isocyanate) werecharged into a glass kettle fitted with a thermometer and overheadstirrer. The charge was brought up to a temperature of 110° C. to 120°C. while mixing and applying vacuum (2 mm mercury (266 Pa)) to removebubbles. The batch was mixed for 10 to 20 minutes after reaching 110° C.to 120° C.

The batch was cast into a heated glass mold that has been preheated inan oven at 140° C. The polymer was cured for 48 hours at 140° C. withoutcatalyst. After curing, the mold was removed from the oven and allowedto cool to room temperature. The plastic sheet was removed from theglass mold and cut into 2″×2″×⅛″ (5.1 cm×5.1 cm×0.3 cm) samples forGardner Impact testing. The initial Gardner impact strength averaged 180in-lbs (21 J).

Example B4

The following components 17.9 grams of 1,4 butanediol, 7.4 grams oftrimethylolpropane and 74.47 grams of DESMODUR W containing 20%trans-trans isomer of 4,4′-methylene-bis-(cyclohexyl isocyanate) werecharged into a glass kettle fitted with a thermometer and overheadstirrer. The charge was brought up to a temperature of 80° C. to 90° C.while mixing and applying vacuum (2 mm mercury (266 Pa)) to removebubbles. The batch was mixed for 1 hour to 2 hours after reaching 80° C.to 90° C. until clear.

The batch was cast into a heated glass mold that has been preheated inan oven at 140° C. The polymer was cured for 48 hours at 140° C. withoutcatalyst. After curing, the mold was removed from the oven and allowedto cool to room temperature. The plastic sheet was removed from theglass mold and cut into 2″×2″×⅛″ (5.1 cm×5.1 cm×0.3 cm) samples forGardner Impact testing. The initial Gardner impact strength averaged10-15 in-lbs (1 J-1.5 J).

Example C

To estimate the overall percentage of aligned crystalline domains insamples of polyurethanes according to the present invention, samples ofFormulation No. 2 (0.7 equivalents of 1,5-pentanediol (PDO), 0.3equivalents of trimethylolpropane (TMP) and 1 equivalent of4,4′-methylene-bis-(cyclohexyl isocyanate) (DESMODUR W)) and FormulationNo. 136 (0.95 equivalents of PDO, 0.05 equivalents of TMP and 1equivalent of 4,4′-methylene-bis-(cyclohexyl isocyanate) (DESMODUR W))were tested using Differential Scanning Calorimetry (DSC) at 2° C./minand Thermogravimetric Analysis (TGA).

Each sample was prepared by mixing all components in the respectiveformulation at about 110° C. for about 30 minutes, degassed under vacuumfor about 5 to about 10 minutes, then casting in a glass mold heated toabout 200° F. (93° C.) for about 48 hours and cooled to room temperature(25° C.) and released from the mold. The sample of Formulation No. 2 wasaged at about 25° C. for about seven months.

The sample of Formulation No. 136 (aged at about 25° C. for about twoweeks) was used as control sample, and its percentage of alignedcrystalline domains was used as a reference for 100% crystallinity. Withrespect to the 100% crystallinity of the sample of Formulation No. 136,the percentage of aligned crystalline domains in Formulation No. 2 wascalculated to be 42%. An endothermic peak at around ˜260° C. was foundfor both samples and attributed to the melting of their ordered domains.The DSC data for each of the samples of Formulation Nos. 2 and 136 arepresented in Table 21 below and in FIGS. 24 and 25, respectively.Thermogravimetric Analysis data (TGA) for a sample of Formulation 136 ispresented in FIG. 26. TABLE 21 Summary of DSC Test Results Sample No.136 2 Equivalents and 0.95 PDO + 0.05 0.7 PDO + 0.3 TMP + 1 TMP + 1Components of Des W Des W Formulation Tg (° C.) 99 Peak Endotherm (° C.)260 260 Heat Capacity (J/g) 3.77 1.63 Estimated Crystalline 100(Control) 42 Domain (%)

Example D

Ballistic Testing

Example D1

A polyurethane polymer according to the present invention was preparedfrom the components listed below in Table 22: TABLE 22 Desired PolymerBatch Size Solids Wt. (g) (g) Monomer Name 1,10- TMP Des W 205.30 300.00decanediol OH # — — — Acid # — — — Equivalent Wt. 87 44.00 131.2Equivalents 0.7 0.3 1.0 desired Mass Monomer 60.90 13.20 131.20 Weight %29.66% 6.43% 63.91% Monomer Monomer masses 88.99 19.29 191.72 forexperiment Weight % Hard 74.40 Segment Weight % 28.74 Urethane MolecularWeight 2053.00 per Crosslink (g/mole) (M_(c))

The 1,10 decanediol, trimethylolpropane and DESMODUR W were preheated to80° C. and added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜115° C. and allowed tocompatibilize. Once clear, the mixture was degassed, and cast into a12″×12″×0.125″ (30.5 cm×30.5 cm 0.3 cm) casting cell preheated to 121°C. The filled cell was cured for 48 hours at 143° C.

This formulation in a 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) thickness passeda 0.40 caliber pistol shot from 30 feet (9.1 m) and 987 ft/sec speedwith no cracking. From 20 feet (6.1 m) the bullet was also stopped andno cracking was observed. Passed multiple 9 mm, 1350 ft/sec (411 m/sec)shots from 20 feet (6.1 m) without cracking. The formulation also passed3 consecutive 12 gauge shotgun shots (1290 ft/sec) from 30 feet (9.1 m)in a ⅜″ thickness (18″×12″×⅜″) (46 cm×30 cm×1 cm) using heavy game leadshot. In each test, the bullets ricocheted off the target.

Example D2

A polyurethane polymer according to the present invention was preparedfrom the components listed below in Table 23: TABLE 23 Polymer DesiredBatch Solids Wt. (g) Size (g) Monomer Name PC- 1,5- TMP Des W 239.04300.00 1733 pentanediol OH # — — — — Acid # — — — — Equivalent Wt. 44052.08 44.00 131.2 Equivalents 0.15 0.55 0.3 1.0 desired Mass 66.00 28.6413.20 131.20 Monomer Weight % 27.61% 11.98% 5.52% 54.89% Monomer Monomer82.83 35.95 16.57 164.66 masses for experiment Weight % 35.84 HardSegment Weight % 24.68 Urethane Molecular 2390.4 Weight per Crosslink(g/mole) (M_(c))

The 1,5 pentanediol, PC-1733, and trimethylolpropane and DESMODUR Wpreheated to 80° C. were added to a glass kettle. Under nitrogen blanketand with constant stirring, the mixture was heated to ˜105° C. andallowed to compatibilize. Once clear, the mixture was degassed, and castinto a 12″×12″×0.125″ (30.5 cm×30.5 cm 0.3 cm) casting cell preheated to121° C. The filled cell was cured for 48 hours at 143° C.

This formulation passed multiple 9 mm, 115 grain, 1350 ft/sec shots by“catching” in bulk of the polymer in a 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm)sample. The bullet penetration was approximately 0.25″ (0.6 cm) with noductile bulge in the back of the sample. The same formulation 4″×4″×1″(10.1 cm×10.1 cm×2.5 cm) sample also passed multiple 0.40 caliber shotsin which the bullet was not caught nor ricocheted. The bullet wassifting, slightly deformed, at the base of the sample. In a ⅜″ (1 cm)thickness, this formulation passed 3 12 gauge shotgun shots from 30 feet(9.1 m). Most of the shot was embedded in the surface of the sample

Example D3

A polyurethane polymer according to the present invention was preparedfrom the components listed below in Table 24: TABLE 24 Desired PolymerBatch Size Solids Wt. (g) (g) Monomer Name 1,4- TMP Des W 175.94 300.00butanediol OH # — — — Acid # — — — Equivalent Wt. 45.06 44.00 131.2Equivalents desired 0.7 0.3 1.0 Mass Monomer 31.54 13.20 131.20 Weight %Monomer 17.93% 7.50% 74.57% Monomer masses 53.78 22.51 223.71 forexperiment Weight % Hard 70.13 Segment Weight % Urethane 33.53 MolecularWeight 1759.42 per Crosslink (g/mole) (M_(c))

The 1,4-butanediol, trimethylolpropane and DESMODUR W preheated to 80°C. were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. Once clear, the mixture was degassed, and cast into a12″×12″×0.125″ (30.5 cm×30.5 cm 0.3 cm) casting cell preheated to 121°C. The filled cell was cured for 48 hours at 143° C.

This formulation in a 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) sample passedmultiple 0.40 caliber shots from 30 feet (9.1 m) with no cracking. Thespeed of the 0.40 caliber was 987 ft/sec (300 m). In ⅜″ thickness at 60ft (18.2 m), it passed multiple 12 gauge shotgun impacts with heavygauge shot at 1290 ft/sec (393 m/sec) muzzle velocity. At 20 ft (6.1 m)and 30 ft (9.1 m), this formulation in 1″ (2.5 cm) thickness broke whenshot with a 9 mm pistol, 115 grain bullet with a speed of 1350 ft/sec(411 m/sec).

Example D4

A polyurethane polymer according to the present invention was preparedfrom the components listed below in Table 25: TABLE 25 Desired PolymerBatch Solids Wt. (g) Size (g) Monomer Name 1,5- TMP Des W 180.85 300.00pentanediol OH # — — — Acid # — — — Equivalent Wt. 52.075 44.00 131.2Equivalents 0.7 0.3 1.0 desired Mass Monomer 36.45 13.20 131.20 Weight %20.16% 7.30% 72.55% Monomer Monomer 60.47 21.90 217.64 masses forexperiment Weight % Hard 70.94 Segment Weight % 32.62 Urethane Molecular1808.53 Weight per Crosslink (g/mole) (M_(c))

The 1,5-pentanediol, trimethylolpropane and DESMODUR W preheated to 80°C. were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜115° C. and allowed tocompatibilize. Once clear, the mixture was degassed, and cast into a12″×12″×0.125″ (30.5 cm×30.5 cm 0.3 cm) casting cell preheated to 121°C. The filled cell was cured for 48 hours at 143° C.

This formulation in a 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) sample passed a0.40 caliber pistol shot from 30 feet (9.1 m) and 987 ft/sec (300 m)speed with no cracking. From 20 feet (6.1 m) the bullet was also stoppedbut some small cracks were observed. Passed multiple 9 mm, 1350 ft/sec(411 m/sec) shots from 20 feet (6.1 m) without cracking. The formulationalso passed 3 consecutive 12 gauge shotgun shots (1290 ft/sec) (393m/sec) from 30 feet (9.1 m) in a ⅜″ (1 cm) thickness using heavy gamelead shot.

Example D5

A polyurethane polymer according to the present invention was preparedfrom the components listed below in Table 26: TABLE 26 Polymer DesiredBatch Solids Wt. (g) Size (g) Monomer Name KM10-1733 1,5-pentanediol TMPDes W 258.44 300.00 OH # — — — — Acid # — — — — Equivalent Wt. 44052.075 44.00 131.2 Equivalents 0.2 0.5 0.3 1.0 desired Mass Monomer88.00 26.04 13.20 131.20 Weight % 34.05% 10.07% 5.11% 50.77% MonomerMonomer 102.15 30.22 15.32 152.30 masses for experiment Weight % Hard44.20 Segment Weight % 22.83 Urethane Molecular Weight 2584.38 perCrosslink (g/mole) (M_(c))

The 1,5 pentanediol, KM10-1733 polycarbonate diol, andtrimethylolpropane and DESMODUR W preheated to 80° C. were added to aglass kettle. Under nitrogen blanket and with constant stirring, themixture was heated to ˜105° C. and allowed to compatibilize. Once clear,the mixture was degassed, and cast into a 12″×12″×0.125″ (30.5 cm×30.5cm 0.3 cm) casting cell preheated to 143° C. The filled cell was curedfor 48 hours at 121° C.

This formulation passed multiple 9 mm, 115 grain, 1350 ft/sec (393m/sec) shots by “catching” in bulk of the polymer in a 6″×6″×1″ (15.2cm×15.2 cm×2.5 cm) sample. The bullet penetration was approximately 0.5″(1.2 cm) with a slight ductile bulge in the back of the sample. The samesample 4″×4″×1″ (10.1 cm×10.1 cm×2.5 cm) also passed multiple 0.40caliber shots in which the bullet was not caught nor ricocheted. It wassitting, slightly deformed at the base of the sample. In a ⅜″ (1 cm)thickness this formulation passed 3-12 gauge shotgun shots from 30 feet(9.1 m). Most of the shot was embedded in the surface of the sample.

All 9 mm shots were 115 grain, 1350 ft/sec (411 m/sec) muzzle velocityshot from a Ruger 9 mm pistol. All 0.40 caliber shots were shot at 987ft/sec (300 m) muzzle velocity from a Smith & Wesson 0.40 caliberpistol. All 12 gauge shotgun shots were shot using a Remington 12 gaugeshotgun using lead shot, heavy game load, at 1290 ft/sec (393 m/sec)muzzle velocity. Samples were shot attached to a 12″ thick wooden blockusing Velcro® with no framing to hold the sample. Shooting was conductedoutdoors at temperatures ranging from about 60° F. (15° C.) to about 80°F. (27° C.).

Example E

Samples prepared from Formulation 2 of Example A above were prepared andtested for Gardner Impact Strength as in Example A above. Sample E1 wasprepared using a 35 weight percent trans, trans isomer of4,4′-methylene-bis-(cyclohexyl isocyanate). Sample E2 was prepared-usinga 17 weight percent trans, trans isomer of4,4′-methylene-bis-(cyclohexyl isocyanate). The Gardner Impact Strengthof Sample E1 was 150 in-lbs (17 J). The Gardner Impact Strength ofSample E2 was 40 in-lbs (5 J). The Sample E1 prepared using a higherweight percentage of trans, trans 4,4′-methylene-bis-(cyclohexylisocyanate) had higher Gardner Impact Strength than Sample E2, which wasprepared using a lower weight percentage of trans, trans4,4′-methylene-bis-(cyclohexyl isocyanate).

Example F

Samples were prepared from Formulation 1 of Example 1 above, furtherincluding 3 weight percent of CIBA TINUVIN B75 liquid light stabilizersystem (commercially available from Ciba Specialty Chemicals)(which is amixture of 20 weight percent IRGANOX 1135, 40 weight percent of TINUVIN571 and 40 weight percent of TINUVIN 765). The initial Gardner ImpactStrength was 75 in-lbs (9 J). After 1000 hours QUV-B, the Gardner ImpactStrength was 75 in-lbs (9 J). The initial tensile strength was 13,400psi (92.4 MPa) and after 1000 hours QUV-B was 13,100 psi (90.3 MPa). Theinitial percent elongation was 40% and after 1000 hours QUV-B was 50%.

Example G Elastoplastic Polyurethane Examples Example G1

The following reactants 131.2 grams of Desmodur W, 13.41 grams oftrimethylolpropane, 26.015 grams of 1,5 pentanediol, and 81.712 gramsStahl KM-1733 1000 molecular weight polycarbonate diol based onhexanediol were mixed together, heated to 80° C. and degassed. Ten ppmof dibutyltindiacetate was added and mixed until the solution washomogeneous. The mixture was poured into a glass mold and cured for 48hours at 290° F. (143° C.). After curing, the cell was allowed to coolto room temperature (25° C.) and the polymer was released from the mold.The polymer had a Young's Modulus of 215,000 psi (about 1482 MPa). Theweight % urethane content was 23.4%. The molecular weight per crosslinkwas 2548 grams/mole. The weight % cyclic content was 32%.

An article of 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) thickness prepared fromthis polymer stopped a 9 mm, 125 grain, bullet shot an initial velocityof 1350 ft/sec (411 m/sec) (from 20 feet (6.1 m) distance by trappingthe bullet in the polymer. The back of the bullet penetratedapproximately ⅛″ (0.3 cm) into the sample with a very small raise on thebackside.

Example G2

The following reactants 131.2 grams of Desmodur W, 13.41 grams oftrimethylolpropane, 28.096 grams of 1,5 pentanediol, and 65.370 gramsStahl KM-1733 1000 molecular weight polycarbonate diol based onhexanediol were mixed together, heated to 80° C. and degassed. Ten ppmof dibutyltindiacetate was added and mixed until the solution washomogeneous. The mixture was poured into a glass mold and cured for 48hours at 290° F. (143° C.). After curing, the cell was allowed to coolto room temperature (25° C.) and the polymer was released from the mold.The polymer had a Young's Modulus of 215,000 psi (about 1482 MPa). Theweight % urethane content was 24.8%. The molecular weight per crosslinkwas 2404 grams/mole. The weight % cyclic content was 34%.

An article of 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) prepared from thispolymer stopped a 9 mm, 125 grain, bullet shot an initial velocity of1350 ft/sec (411 m/sec) from 20 feet (6.1 m) distance by trapping thebullet in the polymer. Four/fifths (⅘) of the length of the bulletpenetrated the sample with the back of the bullet protruding out of theimpacted surface approximately ⅛″ (0.3 cm).

Example G3

The following reactants 131.2 grams of Desmodur W, 13.41 grams oftrimethylolpropane, 28.617 grams of 1,5 pentanediol, and 61.284 gramsStahl KM-1733 1000 molecular weight polycarbonate diol based onhexanediol were mixed together, heated to 80° C. and degassed. Ten ppmof dibutyltindiacetate was added and mixed until the solution washomogeneous. The mixture was poured into a glass mold and cured for 48hours at 290° F. (143° C.). After curing, the cell was allowed to coolto room temperature (25° C.) and the polymer was released from the mold.The polymer had a Young's Modulus of 215,000 psi (about 1482 MPa). Theweight % urethane content was 25.15%. The molecular weight per crosslinkwas 2369 grams/mole. The weight % cyclic content was 34.53%.

An article of 6″×6″×1″ (15.2 cm×15.2 cm×2.5 cm) prepared from thispolymer stopped a 9 mm, 125 grain, bullet shot an initial velocity of1350 ft/sec (411 m/sec) from 20 feet (6.1 m) distance by trapping thebullet. Four/fifths (⅘) of the length of the bullet penetrated thesample with the back of the bullet protruding out of the impactedsurface approximately (0.3 cm).

Poly(ureaurethane) Examples Example G4

The following reactants 318.26 grams of Desmodur W and 0.84 grams oftrimethylolpropane containing 0.5% of dibutyltindiacetate were chargedinto a glass kettle and heated and stirred at 75° C. Deionized water(4.37 grams) was added, mixed, and reacted to form polyurea hardsegments within the polyurethane prepolymer. Carbon dioxide foam wasremoved under vacuum. The temperature was then increased to 80° C. andreacted for 30 minutes. Outgassing was performed using 2 mm mercuryvacuum and 63.42 grams of 1,5 pentanediol was added along with 32.76grams of trimethylolpropane. The mixture was stirred and vacuumincreased slowly. The exothermic temperature reached 95° C. at whichtime the mixture was poured into a 6″×6″×⅛″ (15.2 cm×15.2 cm×0.3 cm)glass mold. The material was cured at 290° F. (143° C.) for 48 hours.The material was released from the mold at room temperature (25° C.)yielding a clear, highly transparent plastic.

Example G5

The following reactants 2.23 grams of trimethylolpropane was reactedwith 76.133 grams of Desmodur W containing 10 ppm of dibutyltindiacetateat 80° C. to formed a branched polyurethane terminated with isocyanategroups. Water (0.9 grams) was added to the batch after the temperaturewas lowered to 60° C., and reacted for 2 hours to form the polyureaportion of the polyurethane polyurea prepolymer. The carbon dioxide wasthen removed with vacuum and 38 grams of trimethylolpropane was added,mixed, degassed under vacuum and poured into a glass mold as describedabove at 75° C. After curing for 48 hours at 290° F. (143° C.), theplastic was removed from the mold at room temperature (25° C.) yieldinga high modulus, highly transparent plastic. The Young's Modulus was441,000 psi measured on an Instron testing machine at a 6″ /minutecrosshead speed.

Example G6

The following reactants 2.23 grams of trimethylolpropane was reactedwith 131.2 grams of Desmodur W using 10 ppm of dibutyltindiacetate byweight of total batch to make a branched, isocyanate-terminatedpolyurethane prepolymer. Deionized water (1.34 grams) was added andreacted at 60° C. The carbon dioxide was removed via vacuum degassing.The temperature was increased to 75° C. and 39.66 grams ofcyclohexanedimethanol was added as a chain extender. After mixing anddegassing, the liquid was poured into a glass mold a described above andcured at 290° F. (143° C.) for 48 hours. Demolding was done at roomtemperature (25° C.) and yielded a high optical quality plastic sheet.

Example H Example H1

A polyurethane was prepared from the following components: DesiredPolymer Batch Size Solids Wt. (g) (g) Monomer Name 1,4- TMP Des W 175.94300.00 butanediol OH # — — — Acid # — — — Equivalent Wt. 45.06 44.00131.2 Equivalents desired 0.7000 0.300 1.000 Mass Monomer 31.54 13.20131.20 Weight % Monomer 17.93% 7.50% 74.57% Monomer masses 53.78 22.51223.71 for experiment

The 1,4-butanediol, trimethylolpropane, and Desmodur W (preheated to 80°C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. Once clear, the mixture was degassed and cast into a12″×12″×0.125″ (30 cm×30 cm×0.3 cm) casting cell preheated to 121° C.The casting was cured for 48 hours at 121° C. and 6 hours at 150° C. Themean Gardner Impact Strength was 102 in-lbs (12 J).

Example H2

A polyurethane was prepared from the following components: PolymerDesired Batch Solids Wt. (g) Size (g) Monomer 1,4- TMP Des W 175.94300.00 Name butanediol OH # — — — Acid # — — — Equivalent 45.06 44.00131.2 Wt. Equivalents 0.7000 0.300 1.000 desired Mass 31.54 13.20 131.20Monomer Weight % 17.93% 7.50% 74.57% Monomer Monomer 53.78 22.51 223.71masses for experiment Weight % 70.13 Hard Segment Weight % 33.53Urethane M_(c) 1759.42

The 1,4-butanediol, trimethylolpropane, and Desmodur W (preheated to 80°C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 110in-lbs (13 J).

Example H3

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name 1,4- TMP Des W 175.94300.00 butanediol OH # — — — Acid # — — — Equivalent Wt. 45.06 44.00131.2 Equivalents desired 0.7000 0.300 1.000 Mass Monomer 31.54 13.20131.20 Weight % Monomer 17.93% 7.50% 74.57% Monomer masses 53.78 22.51223.71 for experiment Weight % Hard 70.13 Segment Weight % Urethane33.53 M_(c) 1759.42

The 1,4-butanediol, trimethylolpropane, and Desmodur W (preheated to 80°C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 131in-lbs (15 J). Desired Polymer Batch Solids Wt. (g) Size (g) MonomerName 1,5- TMP Des W 180.85 300.00 pentanediol OH # — — — Acid # — — —Equivalent Wt. 52.075 44.00 131.2 Equivalents 0.7000 0.300 1.000 desiredMass Monomer 36.45 13.20 131.20 Weight % 20.16% 7.30% 72.55% MonomerMonomer 60.47 21.90 217.64 masses for experiment Weight % Hard 70.94Segment Weight % 32.62 Urethane M_(c) 1808.53

Example H4

The 1,5-pentanediol, trimethylolpropane, and Desmodur W (preheated to80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜115° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 135in-lbs (15 J).

Example H5

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name 1,5- TMP Des W 178.43300.00 pentanediol OH # — — — Acid # — — — Equivalent Wt. 52.075 44.00131.2 Equivalents 0.4000 0.600 1.000 desired Mass Monomer 20.83 26.40131.20 Weight % 11.67% 14.80% 73.53% Monomer Monomer 35.02 44.39 220.59masses for experiment Weight % Hard 41.09 Segment Weight % 33.07Urethane M_(c) 892.15

The 1,5-pentanediol, trimethylolpropane, and Desmodur W (preheated to80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜115° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 71in-lbs (8 J).

Example H6

A polyurethane was prepared from the following components: DesiredPolymer Batch Size Solids Wt. (g) (g) Monomer Name CHDM 1,5- TMP Des W187.86  300.00 pentanediol OH # — — — — Acid # — — — — Equivalent Wt.72.11 52.075 44.00 131.2 Equivalents 0.3500 0.3500 0.300 1.000 desiredMass Monomer 25.24 18.23 13.20 131.20 Weight % 13.43% 9.70% 7.03% 69.84%Monomer Monomer masses 40.30 29.11 21.08 209.51 for experiment Weight %Hard 37.88 Segment Weight % 31.41 Urethane M_(c) 1878.65

The 1,5-pentanediol, CHDM, trimethylolpropane, and Desmodur W (preheatedto 80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 143in-lbs (16 J).

Example H7

A polyurethane was prepared from the following components: PolymerDesired Wt. Batch Solids (g) Size (g) Monomer Name CHDM TMP Des W 194.88352.00 OH # — — — Acid # — — — Equivalent Wt. 72.11 44.00 131.2Equivalents 0.7000 0.300 1.000 desired Mass Monomer 50.48 13.20 131.20Weight % 25.90% 6.77% 67.32% Monomer Monomer masses 91.17 23.84 236.98for experiment Weight % Hard 73.03 Segment Weight % 30.28 Urethane M_(c)1948.77

The CHDM, trimethylolpropane, and Desmodur W (preheated to 80° C.) wereadded to a glass kettle. Under nitrogen blanket and with constantstirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 63in-lbs (7 J).

Example H8

A polyurethane was prepared from the following components: Polymer Wt.Solids (g) Monomer Name CHDM 1,4- TMP Des W 185.41 butanediol OH # — — —— Acid # — — — — Equivalent Wt. 72.11 45.06 44.00 131.2 Equivalents0.3500 0.3500 0.300 1.000 desired Mass Monomer 25.24 15.77 13.20 131.20Weight % 13.61% 8.51% 7.12% 70.76% Monomer Monomer masses 40.84 25.5221.36 212.29 for experiment Weight % Hard 38.38 Segment Weight % 31.82Urethane M_(c) 1854.10

The 1,4-butanediol, CHDM, trimethylolpropane, and Desmodur W (preheatedto 80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 47in-lbs (5 J).

Example H9

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name 1,6- TMP Des W 185.76300.00 hexanediol OH # — — — Acid # — — — Equivalent Wt. 59.09 44.00131.2 Equivalents desired 0.7000 0.300 1.000 Mass Monomer 41.36 13.20131.20 Weight % Monomer 22.27% 7.11% 70.63% Monomer masses 66.80 21.32211.88 for experiment Weight % Hard 71.71 Segment Weight % Urethane31.76 M_(c) 1857.63

The 1,6-hexanediol, trimethylolpropane, and Desmodur W (preheated to 80°C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 130in-lbs (15 J).

Example H10

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name 1,6- 1,4- TMP Des W180.85 300.00 hexanediol butanediol OH # — — — — Acid # — — — —Equivalent Wt. 59.09 45.06 44.00 131.2 Equivalents 0.3500 0.3500 0.3001.000 desired Mass Monomer 20.68 15.77 13.20 131.20 Weight % 11.44%8.72% 7.30% 72.55% Monomer Monomer masses for 34.31 26.16 21.90 217.64experiment Weight % Hard 91.09 Segment Weight % 32.62 Urethane M_(c)1808.53

The 1,6-hexanediol, 1,4-butanediol, trimethylolpropane, and Desmodur W(preheated to 80° C.) were added to a glass kettle. Under nitrogenblanket and with constant stirring, the mixture was heated to ˜115° C.and allowed to compatibilize. The mixture was degassed, and cast into a12″×12″×0.125″ (30 cm×30 cm×0.3 cm) casting cell preheated to 121° C.The casting was cured for 48 hours at 121° C. The mean Gardner ImpactStrength was 53 in-lbs (6 J).

Example H11

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name CHDM 1,6- TMP Des W190.32 300.00 hexanediol OH # — — — — Acid # — — — — Equivalent Wt.72.11 59.09 44.00 131.2 Equivalents 0.3500 0.3500 0.300 1.000 desiredMass Monomer 25.24 20.68 13.20 131.20 Weight % 13.26% 10.87% 6.94%68.94% Monomer Monomer masses for 39.78 32.60 20.81 206.81 experimentWeight % Hard 96.51 Segment Weight % 31.00 Urethane M_(c) 1903.20

The 1,6-hexanediol, CHDM, trimethylolpropane, and Desmodur W (preheatedto 80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜115° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 124in-lbs (14 J).

Example H12

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name 1,4- TMP Des W 185.06532.00 cyclo- hexanediol OH # — — — Acid # — — — Equivalent Wt. 58.0844.00 131.2 Equivalents desired 0.7000 0.300 1.000 Mass Monomer 40.6613.20 131.20 Weight % Monomer 21.97% 7.13% 70.90% Monomer masses 77.3325.11 249.56 for experiment Weight % Hard 71.60 Segment Weight %Urethane 31.88 M_(c) 1850.56

The 1,4-cyclohexanediol, trimethylolpropane, and Desmodur W (preheatedto 80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜95° C. and allowed tocompatibilize. Once clear, the mixture was degassed, and cast into a6″×6″×0.25″ (15 cm×15 cm×0.3 cm) (30 cm×30 cm×0.3 cm) casting cellpreheated to 121° C. The casting was cured for 48 hours at 121° C. TheGardner Impact Strength was 7 in-lbs (1 J).

Example H13

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name Ethylene TMP Des W166.12 300.00 glycol OH # — — — Acid # — — — Equivalent Wt. 31.035 44.00131.2 Equivalents 0.7000 0.300 1.000 desired Mass Monomer 21.72 13.20131.20 Weight % 13.08% 7.95% 78.98% Monomer Monomer masses 39.23 23.84236.93 for experiment Weight % Hard 68.36 Segment Weight % 35.52Urethane M_(c) 1661.25

The ethylene glycol, trimethylolpropane, and Desmodur W (preheated to80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 4in-lbs (4 J).

Example H14

A polyurethane was prepared from the following components: Desired BatchPolymer Size Solids Wt. (g) (g) Monomer Name 1,4- penta- Des W 172.95300.00 butanediol erythritol OH # — — — Acid # — — — Equivalent Wt.45.06 34.04 131.2 Equivalents 0.7000 0.300 1.000 desired Mass Monomer31.54 10.21 131.20 Weight % 18.24% 5.90% 75.86% Monomer Monomer masses54.71 17.71 227.58 for experiment Weight % Hard 71.34 Segment Weight %34.11 Urethane M_(c) 2306.04

The 1,4-butanediol, pentaerythritol, and Desmodur W (preheated to 80°C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜150° C. Thepentaerythritol never dissolved.

Example H15

A polyurethane was prepared from the following components: Desired BatchPolymer Size Solids Wt. (g) (g) Monomer Name 1,4- TMP Des W 192.76300.00 benzene- dimethanol OH # — — — Acid # — — — Equivalent Wt. 69.08544.00 131.2 Equivalents 0.7000 0.300 1.000 desired Mass Monomer 48.3613.20 131.20 Weight % 25.09% 6.85% 68.06% Monomer Monomer masses 75.2620.54 204.19 for experiment 95.81 Weight % Hard 72.73 Segment Weight %30.61 Urethane M_(c) 1927.60

The 1,4-benzenedimethanol, trimethylolpropane, and Desmodur W (preheatedto 80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. The mixture was degassed, and cast into a 12″×12″×0.125″(30 cm×30 cm×0.3 cm) casting cell preheated to 121° C. The casting wascured for 48 hours at 121° C. The mean Gardner Impact Strength was 63in-lbs (7 J).

Example H16

A polyurethane was prepared from the following components: DesiredPolymer Batch Size Solids Wt. (g) (g) Monomer CHDM 1,4- TMP Des W 193.82300.00 Name benzenedimethanol OH # — — — — Acid # — — — — Equivalent72.11 69.085 44.00 131.2 Wt. Equivalents 0.3500 0.3500 0.300 1.000desired Mass 25.24 24.18 13.20 131.20 Monomer Weight % 13.02% 12.48%6.81% 67.69% Monomer Monomer 39.07 37.43 20.43 203.08 masses forexperiment Weight % 98.38 Hard Segment Weight % 30.44 Urethane M_(c)1938.18

The 1,4-benzenedimethanol, CHDM, trimethylolpropane, and Desmodur W(preheated to 80° C.) were added to a glass kettle. Under nitrogenblanket and with constant stirring, the mixture was heated to ˜115° C.and allowed to compatibilize. The mixture was degassed, and cast into a12″×12″×0.125″ (30 cm×30 cm×0.3 cm) casting cell preheated to 121° C.The casting was cured for 48 hours at 121° C. The mean Gardner ImpactStrength was 75 in-lbs (9 J).

Example H17

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer 1,4- 1,4- TMP Des W 184.35300.00 Name benzene- butane- di- diol methanol OH # — — — — Acid # — — —— Equivalent 69.085 45.06 44.00 131.2 Wt. Equiv- 0.3500 0.3500 0.3001.000 alents desired Mass 24.18 15.77 13.20 131.20 Monomer Weight %13.12% 8.55% 7.16% 71.17% Monomer Monomer 39.35 25.66 21.48 213.51masses for ex- periment Weight % 93.16 Hard Segment Weight % 32.00Urethane M_(c) 1843.51

The 1,4-benzenedimethanol, 1,4-butanediol, trimethylolpropane, andDesmodur W (preheated to 80° C.) were added to a glass kettle. Undernitrogen blanket and with constant stirring, the mixture was heated to˜115° C. and allowed to compatibilize. Once clear, the mixture wasdegassed, and cast into a 12″×12″×0.125″ (30 cm×30 cm×0.3 cm) castingcell preheated to 121° C. The casting was cured for 48 hours at 121° C.The Gardner Impact Strength was 62 in-lbs (7 J).

Example H18

A polyurethane was prepared from the following components: PolymerSolids Wt. (g) Monomer Name 1,4- 1,6- TMP Des W 189.26 benzene- hexane-dimethanol diol OH # — — — — Acid # — — — — Equivalent Wt. 69.085 59.0944.00 131.2 Equivalents 0.3500 0.3500 0.300 1.000 desired Mass Monomer24.18 20.68 13.20 131.20 Weight % 12.78% 10.93% 6.97% 69.32% MonomerMonomer masses 38.33 32.78 20.92 207.97 for experiment Weight % Hard95.93 Segment Weight % 31.17 Urethane M_(c) 1892.61

The 1,4-benzenedimethanol, 1,6-hexanediol, trimethylolpropane, andDesmodur W (preheated to 80° C.) were added to a glass kettle. Undernitrogen blanket and with constant stirring, the mixture was heated to˜115° C. and allowed to compatibilize. Once clear, the mixture wasdegassed, and cast into a 12″×12″×0.125″ (30 cm×30 cm×0.3 cm) castingcell preheated to 121° C. The casting was cured for 48 hours at 121° C.The Gardner Impact Strength was 64 in-lbs (7 J).

Example H19

A polyurethane was prepared from the following components: Desired BatchPolymer Size Solids Wt. (g) (g) Monomer Name 4,4′-tri- TMP Des W 213.80300.00 methylene dipiperidine OH # — — — Acid # — — — Equivalent Wt.99.14 44.00 131.2 Equivalents 0.7000 0.300 1.000 desired Mass Monomer69.40 13.20 131.20 Weight % 32.46% 6.17% 61.37% Monomer Monomer masses97.38 18.52 184.10 for experiment Weight % Hard 75.42 Segment Weight %27.60 Urethane M_(c) 2137.98

The 4,4′-trimethylene dipiperidine, TMP and Desmodur W (preheated to 80°C.) were added to a glass kettle. The initial temperature was about 50°C., and when stirred jumped to about 60° C. and gelled into a whitemass.

Example H20

A polyurethane was prepared from the following components: Desired BatchPolymer Size Solids Wt. (g) (g) Monomer Name 1,4- TMP Des W 205.38300.00 bis(hydroxy- ethyl) piperazine OH # — — — Acid # — — — EquivalentWt. 87.12 44.00 131.2 Equivalents 0.7000 0.300 1.000 desired MassMonomer 60.98 13.20 131.20 Weight % 29.69% 6.43% 63.88% Monomer Monomermasses 89.08 19.28 191.64 for experiment Weight % Hard 74.41 SegmentWeight % 28.73 Urethane M_(c) 2053.84

The 1,4-bis(hydroxyethyl)piperazine, trimethylolpropane, and Desmodur W(preheated to 80° C.) were added to a glass kettle. Under nitrogenblanket and with constant stirring, the mixture was heated to ˜105° C.,when the viscosity raised to a point where it could no longer bestirred. The mixture was not clear and non-melted1,4-bis(hydroxyethyl)piperazine was present in the mixture.

Example H21

A polyurethane was prepared from the following components: SolidsMonomer Name N,N′-bis(2- 1,4- TMP Des W hydroxyethyl) butanediol oxamideOH # — — — — Acid # — — — — Equivalent Wt. 88.08 45.06 44.00 131.2Equivalents desired 0.3500 0.3500 0.300 1.000 Mass Monomer 30.83 15.7713.20 131.20 Weight % Monomer 16.14% 8.26% 6.91% 68.69% Monomer massesfor 22.60 11.56 9.68 96.17 experiment — 11.61 4.83 47.94 Weight % HardSegment 40.18 Weight % Urethane 30.89 M_(c) 1909.99

The N,N′-bis(2-hydroxyethyl)oxamide, 1,4-butanediol, trimethylolpropane,and Desmodur W (preheated to 80° C.) were added to a glass kettle. Undernitrogen blanket and with constant stirring, the mixture was heated to˜105° C., when the viscosity raised to a point where it could no longerbe stirred. The mixture was not clear and non-meltedN,N′-bis(2-hydroxyethyl)oxamide was present in the mixture.

Example H22

A polyurethane was prepared from the following components: Desired BatchPolymer Size Solids Wt. (g) (g) Monomer Name 3,6-dithia- TMP Des W208.52 300.00 1,2- octanediol OH # — — — Acid # — — — Equivalent Wt.91.6 44.00 131.2 Equivalents desired 0.7000 0.300 1.000 Mass Monomer64.12 13.20 131.20 Weight % Monomer 30.75% 6.33% 62.92% Monomer masses92.25 18.99 188.76 for experiment — Weight % Hard 74.79 Segment Weight %Urethane 28.29 M_(c) 2085.20

The 3,6-dithia-1,2-octanediol, trimethylolpropane, and Desmodur W(preheated to 80° C.) were added to a glass kettle. Under nitrogenblanket and with constant stirring, the mixture. was heated to ˜105° C.,when the viscosity raised to the point that it could no longer bestirred. The mixture was degassed, and cast into a 6″×6″×0.25″ (15 cm×15cm×0.3 cm) casting cell preheated to 121° C. The casting was cured for48 hours at 121° C. The mean Gardner Impact Strength was 81 in-lbs (9J).

Example H23

A polyurethane was prepared from the following components: PolymerSolids Wt. (g) Monomer 3,6-dithia- bis(4-(2- CHDM TMP Des W 258.90 Name1,2-octanediol hydroxyethoxy)-3,5- dibromophenyl) sulfone OH # — — — — —Acid # — — — — — Equivalent 91.6 326.985 72.11 44.00 131.2 Wt.Equivalents 0.2333 0.2333 0.2333 0.300 1.000 desired Mass 21.37 76.3016.83 13.20 131.20 Monomer Weight % 8.26% 29.47% 6.50% 5.10% 50.68%Monomer Monomer 24.77 88.41 19.50 15.30 152.03 300.00 masses forexperiment Weight % 99.10 Hard Segment Weight % 22.79 Urethane M_(c)2588.96

The 3,6-dithia-1,2-octanediol,bis(4-(2-hydroxyethoxy)-3,5-dibromophenyl)sulfone, CHDM,trimethylolpropane, and Desmodur W (preheated to 80° C.) were added to aglass kettle. Under nitrogen blanket and with constant stirring, themixture was heated to ˜115° C. and allowed to compatibilize. The mixturewas degassed, and cast into a 12″×12″×0.125″ (30 cm×30 cm×0.3 cm)casting cell preheated to 121° C. The casting was cured for 48 hours at121° C.

Example H24

A polyurethane polymer according to the present invention was preparedfrom the components listed below: Polymer Desired Batch Solids Wt. (g)Size (g) Monomer Name 2,2- TMP Des W 187.17 200.00 thiodiethanol OH # —— — Acid # — — — Equivalent Wt. 61.10 44.00 131.2 Equivalents desired0.7000 0.300 1.000 Mass Monomer 42.77 13.20 131.20 Weight % Monomer22.85% 7.05% 70.10% Monomer masses for 45.70 14.11 140.20 experimentWeight % Hard Segment 71.92 Weight % Urethane 31.52 M_(c) 1871.67

The 2,2-thiodiethanol, trimethylolpropane, and Desmodur W (preheated to80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜95° C. and allowed tocompatibilize. Once clear, the mixture was degassed, and cast into a6″×6″×0.25″ (15 cm×15 cm×0.3 cm) casting cell preheated to 121° C. Thecasting was cured for 48 hours at 121° C. The Gardner Impact Strengthwas 5 in-lbs. (1 J) and the sample was brittle.

Example H25

A polyurethane was prepared from the following components: PolymerDesired Batch Solids Wt. (g) Size (g) Monomer Name thiodiethanol 1,4-TMP Des W 181.56 300.00 butanediol OH # — — — — Acid # — — — —Equivalent Wt. 61.1 45.06 44.00 131.2 Equivalents 0.3500 0.3500 0.3001.000 desired Mass Monomer 21.39 15.77 13.20 131.20 Weight % 11.78%8.69% 7.27% 72.26% Monomer Monomer 35.34 26.06 21.81 216.79 masses forexperiment Weight % Hard 37.07 Segment Weight % 32.50 Urethane M_(c)1815.56

The thiodiethanol, 1,4-butanediol, trimethylolpropane, and Desmodur W(preheated to 80° C.) were added to a glass kettle. Under nitrogenblanket and with constant stirring, the mixture was heated to ˜105° C.and allowed to compatibilize. The mixture was degassed, and cast into a12″×12″×0.125″ (30 cm×30 cm×0.3 cm) casting cell preheated to 121° C.The casting was cured for 48 hours at 121° C. The mean Gardner ImpactStrength was 39 in-lbs (4 J).

Example H26

A polyurethane was prepared from the following components: PolymerDesired Batch Solids Wt. (g) Size (g) Monomer Name thiodiethanol 1,6-TMP Des W 186.47 300.00 hexanediol OH # — — — — Acid # — — — —Equivalent Wt. 61.1 59.09 44.00 131.2 Equivalents 0.3500 0.3500 0.3001.000 desired Mass Monomer 21.39 20.68 13.20 131.20 Weight % 11.47%11.09% 7.08% 70.36% Monomer Monomer 34.41 33.27 21.24 211.08 masses forexperiment Weight % Hard 36.09 Segment Weight % 31.64 Urethane M_(c)1864.67

The thiodiethanol, 1,6-hexanediol, trimethylolpropane, and Desmodur W(preheated to 80° C.) were added to a glass kettle. Under nitrogenblanket and with constant stirring, the mixture was heated to ˜105° C.and allowed to compatibilize. The mixture was degassed, and cast into a12″×12″×0.125″ (30 cm×30 cm×0.3 cm) casting cell preheated to 121° C.The casting was cured for 48 hours at 121° C. The mean Gardner ImpactStrength was 55 in-lbs (6 J).

Example H27

A polyurethane was prepared from the following components: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name 1,4- Des N Des W182.80 300.00 butanediol 3400 OH # — — — Acid # — — — Equivalent Wt.45.06 153.00 131.2 Equivalents desired 1.0000 0.300 0.700 Mass Monomer45.06 45.90 91.84 Weight % Monomer 24.65% 25.11% 50.24% Monomer masses73.95 75.33 150.72 for experiment Weight % Hard 96.42 Segment Weight %Urethane 32.28 M_(c) 1828.00

The 1,4-butanediol, Des N 3400 and Desmodur W (preheated to 80° C.) wereadded to a glass kettle. Under nitrogen blanket and with constantstirring, the mixture was heated to ˜105° C. The mixture was degassed,and cast into a 6″×6″×0.25″ (15 cm×15 cm×0.3 cm) casting cell preheatedto 121° C. The casting was cured for 48 hours at 121° C. The meanGardner Impact Strength was 35 in-lbs (4 J).

Example H28

A polyurethane was prepared from the following components: PolymerDesired Batch Solids Wt. (g) Size (g) Monomer Name H₂O 1,4- TMP Des W163.32 300.00 butanediol OH # — — — — Acid # — — — — Equivalent Wt. 9.0145.06 44.00 131.2 Equivalents 0.3500 0.3500 0.300 1.000 desired MassMonomer 3.15 15.77 13.20 131.20 Weight % Monomer 1.93% 9.66% 8.08%80.33% Monomer masses 5.79 28.97 24.25 240.99 for experiment Weight %Hard 79.41 Segment Weight % 36.12 Urethane M_(c) 1633.25

The 1,4-butanediol, TMP, Desmodur W (preheated to 80° C.), and deionizedwater were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜105° C. and allowed tocompatibilize. After compatibilization, condensation (water) wasobserved on the sides of the kettle.

Example H29

A polyurethane was prepared from the following components: EquivalentComponent Weight Equivalents Weight (g) Weight (%) TMP 44.7 0.05 2.2 1.31,4-butanediol 45 0.95 42.8 24.3 Des W 131 1.0 131 74.4

The 1,4-butanediol, TMP and Desmodur W (preheated to 80° C.) were addedto a glass kettle. Under nitrogen blanket and with constant stirring,the mixture was heated to ˜110° C. The mixture was degassed, and castinto a 15″×15″×0.125″ (38 cm×38 cm×0.3 cm) casting cell preheated to121° C. The casting was cured for 48 hours at 121° C. The mean GardnerImpact Strength was 300 in-lbs (35 J). The W_(u) was 33.5%, the W_(c)was 46% and the M_(c) was 10,569 g/mol.

Example H30

A polyurethane was prepared from the following components: EquivalentComponent Weight Equivalents Weight (g) Weight (%) TMP 44.7 0.05 2.2 1.21,5-pentanediol 52 0.95 49.5 27.1 Des W 131 1.0 131 71.7

The 1,5-pentanediol, TMP and Desmodur W (preheated to 80° C.) were addedto a glass kettle. Under nitrogen blanket and with constant stirring,the mixture was heated to ˜110° C. The mixture was degassed, and castinto a 15″×15″×0.125″ (38 cm×38 cm×0.3 cm) casting cell preheated to121° C. The casting was cured for 48 hours at 121° C. The mean GardnerImpact Strength was 400 in-lbs (46 J). The W_(u) was 32.3%, the W_(c)was 44.3% and the M_(c) was 10,973 g/mol.

Example H31

A polyurethane was prepared from the following components: EquivalentComponent Weight Equivalents Weight (g) Weight (%) TMP 44.7 0.05 2.2 1.01,10-decanediol 87 0.95 82.8 38.3 Des W 131 1.0 131 60.6

The 1,10-decanediol, TMP and Desmodur W (preheated to 80° C.) were addedto a glass kettle. Under nitrogen blanket and with constant stirring,the mixture was heated to ˜110° C. The mixture was degassed, and castinto a 15″×15″×0.125″ (38 cm×38 cm×0.3 cm) casting cell preheated to121° C. The casting was cured for 48 hours at 121° C. The mean GardnerImpact Strength was >640 in-lbs (>74 J). The W_(u) was 27.3%, the W_(c)was 37.5% and the M_(c) was 12,974 g/mol. The Dynatup Impact Strengthwas 77 Joules.

Example H32

A polyurethane was prepared from the following components: EquivalentComponent Weight Equivalents Weight (g) Weight (%) TONE 210 406.4 0.281.3 32.3 1,5-pentanediol 52 0.5 26.0 10.3 TMP 44.7 0.3 13.4 5.3 Des W131 1.0 131 52.0

The TONE 210, 1,5-pentanediol, TMP and Desmodur W (preheated to 80° C.)were added to a glass kettle. Under nitrogen blanket and with constantstirring, the mixture was heated to ˜110° C. The mixture was degassed,and cast into a 15″×15″×0.125″ (38 cm×38 cm×0.3 cm) casting cellpreheated to 121° C. The casting was cured for 48 hours at 121° C. TheW_(u) was 23.4%, the W_(c) was 32% and the M_(c) was 2542 g/mol.

Example H33

A polyurethane was prepared from the following components: EquivalentComponent Weight Equivalents Weight (g) Weight (%) TONE 210 406.4 0.1561.0 26.1 1,5-pentanediol 52 0.55 28.6 12.2 TMP 44.7 0.3 13.4 5.7 Des W131 1.0 131 56.0

The Tone 210, 1,5-pentanediol, TMP and Desmodur W (preheated to 80° C.)were added to a glass kettle. Under nitrogen blanket and with constantstirring, the mixture was heated to ˜110° C. The mixture was degassed,and cast into a 15″×15″×0.125″ (38 cm×38 cm×0.3 cm) casting cellpreheated to 121° C. The casting was cured for 48 hours at 121° C. TheW_(u) was 25.2%, the W_(c) was 34.6% and the M_(c) was 2342 g/mol.

Example I

Samples of Formulations 1-10 of Example A, Plexiglas from McMasterCarr,Poly 84 stretched acrylic and commercial grade LEXAN were tested forK-factor according to the following conditions:

-   Load cell: 2000 lb_(f)-   Humidity(%): 50-   Temperature: 73° F. (23° C.)-   Test Speed: 320 lb^(f)/min

Thickness: 0.120″ Thickness Crack Test # Sample ID Width (in.) (in.)(in.) Load (lbs) Time (sec) K Factor 34 1A 2.138 0.123 0.575 345.800345.800 1296.220 36 1B 2.144 0.122 0.600 318.400 318.400 1241.140 35 1C2.135 0.128 0.700 294.200 294.200 1199.424 31 2A 1.995 0.123 0.750304.400 304.400 1477.415 33 2B 1.990 0.131 0.650 322.100 322.1001330.586 32 2C 1.965 0.132 0.750 278.700 278.700 1279.169 29 3A 1.9860.125 0.475 216.400 216.400 777.079 30 3B 1.972 0.130 0.425 228.200228.200 746.028 1 3C 1.988 0.127 0.750 175.600 117.067 822.370 26 4A2.017 0.125 0.600 327.500 327.500 1321.788 27 4B 2.009 0.120 0.750276.500 276.500 1359.195 28 4C 2.023 0.123 0.675 283.500 283.5001259.891 24 5A 2.023 0.122 0.600 20.9.4 157.050 866.505 23 5B 2.0200.120 0.750 179.900 107.940 874.598 25 5C 2.056 0.166 0.700 205.100205.100 967.357 14 6A 2.053 0.124 0.650 291.000 218.250 1225.187 16 6B2.039 0.122 0.670 245.900 245.900 1086.512 15 6C 2.068 0.127 0.690271.100 232.371 1144.531 12 7A 2.024 0.127 0.620 277.600 185.0671125.576 13 7B 2.034 0.130 0.750 288.300 192.200 1288.378 11 7C 2.0190.128 0.750 278.700 101.345 1276.297 10 8A 2.006 0.124 0.960 238.400158.933 1388.038 9 8B 2.021 0.124 0.800 284.600 87.569 1402.845 2 8C2.009 0.118 0.750 355.400 266.550 1776.120 6 9A 2.003 0.118 0.5201179.000 428.727 4681.823 8 9B 2.020 0.123 0.670 345.800 106.4001525.675 7 9C 1.992 0.118 0.450 1220.000 395.676 4486.874 3 10A  2.0100.116 0.750 782.300 586.725 3956.318 4 10B  2.021 0.119 0.450 742.600270.036 2655.849 5 10C  2.023 0.119 0.450 756.000 274.909 2700.237 2111A  2.011 0.132 0.650 272.200 98.982 1106.454 22 11B  2.006 0.130 0.650220.700 115.148 910.576 20 11C  2.011 0.130 0.650 255.000 78.4621048.797 19 12A  2.019 0.134 0.650 873.600 268.800 3470.984 17 12B 2.021 0.132 0.680 798.900 290.509 3313.758 18 12C  2.023 0.133 0.710863.400 313.964 3655.555 37 13A  2.036 0.125 1.500 1435.000 521.81815960.663 38 13B  2.024 0.126 1.500 1401.000 262.688 15670.107 39 13C 2.024 0.133 1.500 1456.000 273.000 15489.381

Example J

A polyurethane was prepared from the following components: Desired BatchSize Solids Polymer Wt. (g) (g) Monomer Name 1,5-pentanediol TMP Des W2100.00 OH # — — — Acid # — — — Equivalent Wt. 52.075 44.00 131.2Equivalents 0.4000 0.600 1.000 desired Mass Monomer 20.83 26.40 131.20178.43(sum) Weight % 11.67% 14.80% 73.53% Monomer Monomer masses 245.15310.71 1544.13 for experiment Weight % Hard 41.09 0.4(131 + 52)/ Segment178.43 Weight % 33.07 59 g/eq./ Urethane 178.43 g/eq. M_(c) 892.15178.43/ 0.2 moles TMP

The 1,5-pentanediol, trimethylolpropane, and Desmodur W (preheated to80° C.) were added to a glass kettle. Under nitrogen blanket and withconstant stirring, the mixture was heated to ˜115° C. and allowed tocompatibilize. Once clear, the mixture was degassed, and cast into a14″×14″×0.375″ casting cell preheated to 121° C. A first set of sampleswas cured for 48 hours at 121° C. A second set of samples was cured for48 hours at 121° C. and for 12 hours at 145° C. Each set of samples wasevaluated for stress craze resistance by immersion for 30 minutes in 75%aqueous solution of sulfuric acid. The second set of samples passed 30minutes at 4000 psi.

Example K

Trimethylolpropane (0.05 equivalents), 1,10-decanediol (0.95equivalents) and DESMODUR W (1.0 equivalents, preheated to 80° C.) wereadded to a glass kettle. Under nitrogen blanket and with constantstirring, the mixture was heated to 110° C. and allowed tocompatibilize. Once clear, the mixture was degassed, and cast into a12″×12″×0.125″ casting cell preheated to 143° C. The filled cell wascured for 48 hours at 121° C. The Dynatup Multiaxial Impact Strength was77 Joules, measured in accordance with ASTM-D 3763-02. The DynatupMultiaxial Impact Strength of a sample of Lexan was 72 Joules.

Example L

An isocyanate functional urethane prepolymer was prepared by reactingusing 0.3 equivalents of 1,5-pentanediol, 1.0 equivalent of Desmodur Wand 10 ppm dibutyltin diacetate as reactants in a glass kettle undervacuum. The reaction temperature was maintained at 143° C. for 10 hoursand 0.4 equivalents of 1,5-pentanediol and 0.3 equivalents oftrimethylolpropane were added. After about 30 minutes at 110° C., themixture was cast between release coated glass molds and cured for 72hours at 290° F. (143° C.). The mold was removed from the oven and theplastic released. The Gardner Impact strength was 256 in-lbs (29 J).

An isocyanate functional urethane prepolymer was prepared by reactingusing 0.5 equivalents of 1,5-pentanediol and 1.0 equivalent of DesmodurW and 10 ppm dibutyltin diacetate as reactants in a glass kettle undervacuum. The reaction temperature was maintained at 143° C. for 10 hoursand 0.2 equivalents of 1,5-pentanediol and 0.3 equivalents oftrimethylolpropane were added. After about 30 minutes at 110° C., themixture was cast between release coated glass molds and cured for 72hours at 290° F. (143° C.). The mold was removed from the oven and theplastic released. The Gardner Impact strength was 256 in-lbs (29 J).

The sample prepared from an isocyanate functional urethane prepolymerhaving a higher amount (0.5 equivalents) of 1,5-pentanediol had a higherGardner Impact strength. While not intending to be bound by any theory,it is believed that the miscibility between the components is improvedby pre-reacting a portion of the short chain diol with thepolyisocyanate.

Examples M Example M1

An isocyanate functional prepolymer (NCO/OH ratio of 3.8) having anequivalent weight of 327 grams/mole was prepared by reacting thefollowing components: Equivalent. Number of Component Weight % Wt.equivalents DESMODUR W 54.42 131.2 0.42 4,4′-methylene-bis- (cyclohexylisocyanate) DBT FASTCAT 4202 0.005 (dibutyl tin dilaurate) PLURACOLE400NF 5.095 200 0.03 (polyethylene glycol) PLURONIC L62D 33.97 11800.03 (ethylene oxide/propylene oxide block copolymer) TRIMETHYLOPROPANE2.32 45 0.05 CAPA 2077A 1.23 375 0.003 polycaprolactone polyol IRGANOX1010 0.49 CYASORB UV 5411 0.97 TINUVIN 328 1.46 IRGANOX MD 1024 0.05Total 100.000000at a temperature of about 104° C. for about 5 hours. All of thecomponents were mixed together, except the stabilizers which weredissolved after the prepolymer was reacted.

About 9 grams of acrylamide was dissolved in about 45 grams of1,4-butanediol at a temperature of about 25° C. and mixed with about 365grams of the above prepolymer and about 0.1 weight percent ofazobisisobutyronitrile (AIBN) based on total solids. The mixture wascast into a glass mold and heated in an oven at a temperature of about80° C. for about 48 hours with constant stirring. A clear polymerizatewas formed. A sample of the cured polymer was evaluated for lighttransmittance and Gardner Impact Strength. The light transmittance ofthe sample was 91% and the Gardner Impact Strength was 150 in-lbs (17J).

Example M2

A polyurethane polymer according to the present invention was preparedfrom the above isocyanate functional prepolymer, cyclohexanedimethanol(CHDM) and 1,4-butanediol as listed below: Desired Polymer Batch SolidsWt. (g) Size (g) Monomer Prepolymer CHDM 1,4- 417.53 200.00 Namebutanediol OH # — — — Acid # — — — Equivalent 365.71 72.11 45.06 Wt.Equivalents 1.00 0.25 0.75 desired Mass 365.71 18.03 33.80 MonomerWeight % 87.59% 4.32% 8.09% Monomer Monomer 175.18 8.64 16.19 masses forexperiment

The prepolymer, CHDM (preheated to 80° C.) and 1,4-butanediol were addedto a glass kettle. Under nitrogen blanket and with constant stirring,the mixture was heated to ˜40° C. and allowed to compatibilize. Onceclear, the mixture was degassed, and cast into a 6″×6″×0.25″ (15 cm×15cm×0.6 cm) casting cell and aluminum cups preheated to 80° C. The filledcell was cured for 24 hours at 121° C.

An article of 6″×6″×1″ thickness (15 cm×15 cm×2.5 cm) prepared from thispolymer stopped a 9 mm, 125 grain, bullet shot an initial velocity of1350 ft/sec (411 m/sec) from 20 feet (6.1 m) distance with littlesurface damage. The same sample also withstood a 0.40 caliber shot withlittle surface damage. The bullets did not ricochet or embed in thepolymer. The bullets were laying partly deformed at the bottom of thesample.

Example M3

A polyurethane polymer according to the present invention was preparedfrom the above isocyanate functional prepolymer, cyclohexanedimethanol(CHDM) and 1,4-butanediol as listed below: Desired Polymer Batch SolidsWt. (g) Size (g) Monomer Name Prepolymer CHDM 1,4- 424.30 200.00butanediol OH # — — — Acid # — — — Equivalent Wt. 365.71 72.11 45.06Equivalents 1.00 0.50 0.50 desired Mass Monomer 365.71 36.06 22.53Weight % 86.19% 8.50% 5.31% Monomer Monomer 172.38 17.00 10.62 massesfor experiment

The prepolymer, CHDM (preheated to 80° C.) and 1,4-butanediol were addedto a glass kettle. Under nitrogen blanket and with constant stirring,the mixture was heated to ˜40° C. and allowed to compatibilize. Onceclear, the mixture was degassed, and cast into a 6″×6″×0.25″ (15 cm×15cm×0.6 cm) casting cell and aluminum cups preheated to 80° C. The filledcell was cured for 24 hours at 121° C.

Example M4

A polyurethane polymer according to the present invention was preparedfrom the above isocyanate functional prepolymer and hydroquinonebis(hydroxyethyl)ether as listed below: Desired Polymer Batch Solids Wt.(g) Size (g) Monomer Name Prepolymer Hydroquinone 483.40 250.00bis(hydroxyethyl) ether OH # — — Acid # — — Equivalent Wt. 384.29 99.11Equivalents desired 1.00 1.00 Mass Monomer 384.29 99.11 Weight % Monomer79.50% 20.50% Monomer masses 198.74 51.26 for experiment

The prepolymer and hydroquinone bis(hydroxyethyl)ether were added to aglass kettle and placed in a heating mantle. Under nitrogen blanket andwith constant stirring, the mixture was heated to ˜85° C. and allowed tocompatibilize. Once clear, the mixture was placed under vacuum anddegassed, and cast into a 6″×6″×0.25″ (15 cm×15 cm×0.6 cm) casting cellpreheated to 80° C. The filled cell was cured for 24 hours at 121° C.The cast sample was clear, but showed some haze. The Gardner ImpactStrength was 320 in-lbs (37 J).

Example N

An isocyanate functional prepolymer was prepared by reacting thefollowing components: Equivalent. Number of Component Weight % Wt.equivalents DESMODUR W 54.42 131.2 0.42 4,4′-methylene-bis- (cyclohexylisocyanate) DBT FASTCAT 4202 0.005 (dibutyl tin dilaurate) PLURACOLE400NF 5.095 200 0.03 (polyethylene glycol) PLURONIC L62D 33.97 11800.03 (ethylene oxide/propylene oxide block copolymer) TRIMETHYLOPROPANE2.32 45 0.05 CAPA 2077A 1.23 375 0.003 polycaprolactone polyol Total100.000000at a temperature of about 104° C. for about 5 hours. All of thecomponents were mixed together, except the stabilizers which weredissolved after the prepolymer was reacted.

A polyurethane polymer according to the present invention was preparedfrom the above prepolymer and 1,4-butanediol as listed below: DesiredPolymer Batch Solids Wt. (g) Size (g) Monomer Name Prepolymer1,4-butanediol 375.38 100.00 OH # — — Acid # — — Equivalent Wt. 330.3245.06 Equivalents 1.00 1.00 desired Mass Monomer 330.32 45.06 Weight %Monomer 88.00% 12.00% Monomer masses 88.00 12.00 for experiment

The prepolymer and 1,4-butanediol were added to a glass kettle. Undernitrogen blanket and with constant stirring, the mixture was heated to˜45° C. and allowed to compatibilize. Once clear, the mixture wasdegassed, and cast into a 4″×4″×60 mil casting cell preheated to 80° C.The filled cell was cured for 24 hours at 121° C.

An article of 6″×6″×1″ (15 cm×15 cm×2.5 cm) prepared from this polymerstopped a 9 mm, 125 grain, bullet shot an initial velocity of 1350ft/sec (411 m/sec) from 20 feet (6.1 m) distance with little surfacedamage. The same sample also withstood a 0.40 caliber shot with littlesurface damage.

Examples O Example O1

An isocyanate functional prepolymer was prepared by reacting thefollowing components: Prepolymer Formulation Equivalent NormalizedNormalized Wt. Component weight Equivalents Wt. (g) Weight % Equivalentsto Des W (g) CAPA 2047 200.0 0.14 27.8 27.8% 0.28 56.68 CAPA 2077 375.00.018 6.65 6.7% 0.036 13.56 TMP 44.6 0.027 1.2 1.2% 0.055 2.45 OH Totals= — 0.18 35.65 — 0.37 72.69 Des W 131.2 0.49 64.35 64.4% 1.0000 131.20Total = 78.5% Prepolymer M_(w) = 203.89 Prepolymer W_(urethane) = 28.94%Prepolymer M_(c) = 11150 Prepolymer W_(b) = 7433at a temperature of about 104° C. for about 5 hours. All of thecomponents were mixed together, except the stabilizers which weredissolved after the prepolymer was reacted.

A polyurethane polymer according to the present invention was preparedfrom the above prepolymer and CHDM as listed below: Desired BatchPolymer Size Solids Wt. (g) (g) Monomer Name Prepolymer CHDM 402.98800.00 OH # — — Acid # — — Equivalent Wt. 330.87 72.11 Equivalents 1.001.0000 desired Mass Monomer 330.87 72.11 Weight % 82.11% 9.01% MonomerMonomer masses 656.85 143.15 for experiment

The prepolymer and CHDM were added to a glass kettle. Under nitrogenblanket and with constant stirring, the mixture was heated to ˜55° C.and allowed to compatibilize. Once clear, the mixture was degassed, andcast into a 13″×13″×0.25″ casting cell preheated to 80° C. The filledcell was cured for 24 hours at 121° C.

Example O2

A polyurethane polymer according to the present invention was preparedfrom the above prepolymer and CHDM as listed below: Desired PolymerBatch Solids Wt. (g) Size (g) Monomer Name Prepolymer 2,2-thiodiethanol391.97 700.00 OH # — — Acid # — — Equivalent Wt. 330.87 61.10Equivalents desired 1.00 1.0000 Mass Monomer 330.87 61.10 Weight %Monomer 84.41% 15.59% Monomer masses 590.89 109.11 for experiment

The prepolymer and 2,2-thiodiethanol were added to a glass kettle. Undernitrogen blanket and with constant stirring, the mixture was heated to˜55° C. and allowed to compatibilize. Once clear, the mixture wasdegassed, and cast into a 13″×13″×0.25″ casting cell preheated to 80° C.The filled cell was cured for 24 hours at 121° C.

Example P

As a comparative example, a thermoplastic polymer was prepared using 1.0equivalent of 1,10-decanediol and 1.0 equivalent of Desmodur W asreactants and 10 ppm dibutyltindiacetate as catalyst. The polymer wasmixed at 110° C. in a glass kettle under vacuum. After about 30 minutesat 110° C., the mixture was cast between release coated glass molds andcured for 72 hours at 290° F. (143° C.). The mold was removed from theoven and the plastic released. The Gardner Impact strength was less than40 in-lbs (5 J) and averaged about 16 in-lbs (2 J).

A polymer according to the present invention was prepared in a similarmanner using a small amount of a branched polyol, namely 0.05equivalents of trimethylolpropane, as well as 0.95 equivalents of1,10-decanediol, and 1.0 equivalents of Desmodur W. The Gardner impactstrength averaged 640-in-lbs for this branched thermoplastic with amolecular weight per crosslink of about 12,900 grams/mole.

Example Q Comparative Example

For comparison, a prepolymer was prepared by reacting about 0.1equivalents of trimethylol propane with about 1.0 equivalent of4,4′-methylene-bis-(cyclohexyl isocyanate) (DESMODUR W) to form apolyurethane polyisocyanate dissolved in an excess (0.9 eqs.) ofDESMODUR W. About 10 ppm of dibutyltindiacetate was used as a catalyst.While mixing rapidly at room temperature, about 0.1 equivalents of4,4′-methylene-bis-cyclohexylamine, a diamine analog of DESMODUR W, wasadded. Immediately, a white, flaky precipitate formed. The precipitateincreased in concentration sitting overnight and would not dissolve uponheating up to about 290° F. (143° C.). The above example was repeated inthe same order as above, but the polyisocyanate was heated to about 40°C. While mixing rapidly, the diamine was added and a similar whiteprecipitate formed which could not be dissolved upon heating up to about290° F. (143° C.).

According to the present invention, the same polyisocyanate above washeated to about 40° C. About 0.1 equivalents of water was added whilemixing rapidly. Vacuum was applied (4 mm Hg) to remove the carbondioxide and a polyurea formed within the polyurethane to form apolyurethane polyurea polyisocyanate that was slightly hazy. The diamineanalog of DESMODUR W was formed in situ when the water was reacted. Thismixture was then reacted with 0.8 equivalents of trimethylolpropane toform a high modulus plastic with high optical clarity. The lighttransmittance of a ⅛″ thick (0.3 cm) sample was 91.8% with less than0.1% haze. The glass transition temperature was 175° C.

According to the present invention, the same polyisocyanate was reactedwith 0.2 equivalents of water at about 40° C. and the carbon dioxideremoved via vacuum. The diamine analog of DESMODUR W was formed in situwhen the water was reacted. About 0.5 equivalents of pentanediol andabout 0.2 equivalents of trimethylolpropane were reacted with thepolyurethane polyurea polyisocyanate to form a high clarity opticalplastic with a light transmittance of 91.74% for a ⅛″ thick (0.3 cm)sample and a glass transition temperature of about 137° C.

Examples R Example R1

In a glass kettle under nitrogen blanket with stirring, were charged8.26 weight % 3,6-dithia-1,2-octanediol (91.6 equivalent wt.); 29.47weight % bis(4-(-hydroxyethoxy)-3,5-dibromophenyl)sulfone (326.985equivalent wt.); 6.50 weight % 1,4-cyclohexanedimethanol (CHDM) (72.1equivalent wt.); 5.10 weight % trimethylolpropane (TMP) (44 equivalentwt.); 50.68 weight % 4,4′-methylenebis (cyclohexyl isocyanate) (DESMODURW) (131.2 equivalent wt.) preheated to a temperature of 80° C. Themixture was heated to a temperature of 115° C.

The mixture was then degassed and cast into a 12″×13″×0.125″ (30 cm×33cm×0.3 cm) casting cell which had been preheated to a temperature of121° C. The filled cell was then cured in an oven for a period of 48hours at 121° C.

The refractive index of the resulting lens was measured as n_(D)=1.5519.

Example R2

In a glass kettle under nitrogen blanket with stirring, were charged30.75 weight % 3,6-dithia-1,2-octanediol (91.6 equivalent wt.); 6.23weight % TMP (44.0 equivalent wt.) and 62.92 weight % DESMODUR W (131.2equivalent wt.) which was preheated to a temperature of 80° C. Themixture was heated to a temperature of 105° C.

The mixture was then degassed and cast into a 12″×13″×0.125″ (30 cm×33cm×0.3 cm) casting cell which had been preheated to a temperature of121° C. The filled cell was then cured in an oven for a period of 48hours at 121° C.

The refractive index of the resulting lens was measured as n_(D)=1.5448and the impact as 82.0 in-lbs (9 J).

Example R3

In a glass kettle under nitrogen blanket with stirring, were charged9.70 weight % 1,5-pentanediol (52.1 equivalent wt.); 7.03 weight % TMP(44.0 equivalent wt.); 13.43 weight % CHDM (72.1 equivalent wt.) and69.84% DESMODUR W (131.2 equivalent wt.) which was preheated to atemperature of 80° C. The mixture was heated to a temperature of 105° C.

The mixture was then degassed and cast into a 12″×13″×0.125″ (30 cm×33cm×0.3 cm)casting cell which had been preheated to a temperature of 121°C. The filled cell was then cured in an oven for a period of 48 hours at121° C.

The impact was measured as 160.0 in-lbs (18 J).

Example R4

This example was conducted in accordance with the procedure in Example 3with the exception that 1,4-butanediol (45.1 equivalent wt.) was usedinstead of 1,5 pentanediol and CHDM was not present in the mixture.17.28% 1,4 butanediol, 7.23% trimethylolpropane, and 75.48% DESMODUR W.

The impact was measured as 120.0 in-lbs (14 J).

Example R5

This example was conducted in accordance with the procedure in Example 4with the exception that 1,4-benzenedimethanol (69.1 equivalent wt.) wasused instead of 1,4-butanediol. 25.09 weight % 1,4benzenedimethanol,6.85 weight % trimethylolpropane, and 74.57 weight %DESMODUR W.

The impact was measured as 72.0 in-lbs (8 J). It was observed that afterfifteen minutes into the cure cycle, the material turned hazy. Thus, theoven temperature had been increased to 143° C. for the remainder of thecure cycle, but the material remained hazy.

Example R6

This example was conducted in accordance with the procedure in Example 5with the exceptions that 1,4-butanediol (45.1 equivalent weight) wasalso added to the mixture and the mixture was heated to a temperature of115° C. instead of 105° C. 13.12 weight % 1,4 benzenedimethanol, 8.55weight % 1,4 butanediol, and 71.17 weight % DESMODUR W

The impact was measured as 72.0 in-lbs (8 J).

Example R7

This example was conducted in accordance with the procedure in Example 6with the exception that 1,6-hexanediol (59.1 equivalent wt.) was usedinstead of 1,4-butanediol. 12.76 weight % 1,4 benzenedimethanol, 10.93weight % 1,6 hexanediol, and 69.32 weight % DESMODUR W.

The impact was measured as 64.0 in-lbs (7 J).

Example R8

This example was conducted in accordance with the procedure in Example 7with the exceptions that thiodiethanol (61.1 equivalent wt.) was usedinstead of 1,4-benzenedimethanol and the mixture was heated to atemperature of 105° C. instead of 115° C. 11.78 weight %2,2-thiodiethanol, 8.69 weight % 1,4 butanediol, 7.27 weight %trimethylolpropane, and 70.10 weight % DESMODUR W.

The impact was measured as 72.0 in-lbs (8 J).

Example R9

This example was conducted in accordance with the procedure in Example 3with the exceptions that CHDM was not present in the mixture and themixture was heated to a temperature of 115° C. instead of 105° C. 20.16weight % 1,5 pentanediol, 7.3 weight % trimethylolpropane, and 72.55weight % DESMODUR W.

The impact was measured as 200.0 in-lbs (23 J).

Example R10

This example was conducted in accordance with the procedure in Example 9with the exception that 1,8-octanediol (73.1 equivalent wt.) was usedinstead of 1,5-pentanediol. 26.14 weight % 1,8 octanediol, 6.75 weight %trimethylol propane, and 67.11 weight % DESMODURW.

The impact was measured as 624.0 in-lbs (72 J).

Example R11

This example was conducted in accordance with the procedure in Example10 with the exception that 1,10-decanediol (87.1 equivalent wt.) wasused instead of 1,8-octanediol. 29.66 weight % 1,10 decanediol, 6.43weight % trimethylolpropane, and 63.9 weight % DESMODUR W.

The impact was measured as 624.0 in-lbs (72 J).

Example R12

This example was conducted in accordance with the procedure in Example11 with the exceptions that ethyleneglycol (31.0 equivalent wt.) wasused instead of 1,10-decanediol and the mixture was heated to atemperature of 105° C. instead of 115° C. 13.06 weight % ethyleneglycol, 7.95 weight % trimethylolpropane, and 78.99 weight % DESMODUR W

The impact was measured as 8.0 in-lbs (1 J).

Example R13

This example was conducted in accordance with the procedure in Example11 with the exception that 1,12-dodecanediol was used instead of1,10-decanediol. 32.87 weight % 1,12 dodecanediol, 6.14 weight %trimethylolpropane, and 60.99 weight % DESMODUR W.

The impact was measured as 624.0 in-lbs (72 J).

Example R14

This example was conducted in accordance with the procedure in Example13 with the exceptions that 1,6-hexanediol (59.1 equivalent wt.) wasused instead of 1,12-dodecanediol and the mixture was heated to atemperature of 105° C. instead of 115° C. 22.24 weight % 1,6 hexanediol,7.11 weight % trimethylolpropane, and 70.65 weight % DESMODUR W.

The impact was measured as 144 in-lbs (17 J).

Example R15

This example was conducted in accordance with the procedure in Example9. The impact was measured as 80.0 in-lbs (9 J).

Example R16

This example was conducted in accordance with the procedure in Example11 with the exceptions that 101.2 equivalent wt of 1,10-decanediol wasused; and KM-1733 (a 1000 MW carbonate diol made from hexanediol anddiethylcarbonate, and commercially available from ICI) (428 equivalentwt.) was added to the mixture. 28.29% 1,10 decanediol, 9.48 weight %PC-1733, 5.69 weight % trimethylolpropane, and 56.54 weight % DESMODURW.

The impact was measured as 640.0 in-lbs (74 J).

Example R17

Formulations 1 through 11 were prepared in accordance with the procedureof Example 3 with the exception that the components listed in Table 21were used to prepare the reaction mixture. The resultant properties(including tensile strength at yield, % elongation at yield, tensilestrength at break, % elongation at break, and Young's Modulus weremeasured in accordance with ASTM-D 638-03; Gardner Impact was measuredin accordance with ASTM-D 5420-04; Tg was measured using DynamicMechanical Analysis; and Density was measured in accordance with ASTM-D792) of formulations 1 through 11 are shown in Tables 27-29. TABLE 27Equivalent Wt. Formulation # Component (g/Eq.) Equivalents Weight Weight% Wu (%) Wc (%) Mc (g/mole) 1 TMP 44.7 0.3 13.40 6.5 28.7 39.4 2055 1,10dodecanediol 87.1 0.7 60.97 29.7 DESMODUR W 131.0 1.0 131.0 63.8 2 TMP44.7 0.3 13.40 6.7 29.4 40.4 2006 1,10 dodecanediol 87.1 0.35 30.48 15.21,8 octanediol 73.1 0.35 25.58 12.7 DESMODUR W 131.0 1.0 131.0 65.4 3TMP 44.7 0.3 13.40 7.61 33.5 46.04 1759 1,4 butanediol 45.0 0.7 31.517.9 DESMODUR W 131.0 1.0 131.0 74.49 4 TMP 44.7 0.3 13.40 7.40 32.644.8 1808 1,5 pentanediol 52.0 0.7 36.4 20.13 DESMODUR W 131.0 1.0 131.072.47 5 TMP 44.7 0.6 26.82 11.64 33.0 45.81 1786 1,5 pentanediol 52.00.4 20.8 15.06 DESMODUR W 131.0 1.0 131.0 73.3 6 TMP 44.7 0.3 13.40 7.2031.77 43.62 1857 1,6 hexanediol 59.0 0.7 41.3 22.26 DESMODUR W 131.0 1.0131.0 70.54 7 TMP 44.7 0.3 13.40 6.81 30.44 1938 1,4 CHDM 72.11 0.3525.24 13.02 1,6 BDM 69.08 0.35 24.18 12.48 DESMODUR W 131.0 1.0 131.0131.0

TABLE 28 Equivalent Wt. Wu Wc Mc Formulation # Component (g/Eq.)Equivalents Weight Weight % (%) (%) (g/mole) 8 TMP 44.7 0.3 13.40 7.0331.41 43.1 1879 1,4 CHDM 72.11 0.35 25.24 13.43 1,5 52.0 0.35 18.23 9.70pentanediol 9 TMP 44.7 0.3 13.40 6.94 31.0 42.55 1903 1,4 CHDM 72.110.35 25.24 13.26 1,6 59.09 0.35 20.68 10.87 hexanediol DESMODUR W 131.01.0 131.0 68.94 10 TMP 44.7 0.3 13.20 6.7 30.2 41.4 1956 1,8 73.1 0.751.17 26.2 octanediol DESMODUR W 131.0 1.0 1.0 67.1 11 TMP 44.7 0.313.40 6.33 28.29 38.84 2085 3,6-dithia-1,2 91.6 0.7 64.12 30.75octanediol DESMODUR W 131.0 1.0 131.0 62.92Note:Formula 11 has a refractive index of 1.55 and a Gardner Impact strengthof 65 in-lbs.

TABLE 29 Tensile % Tensile % Strength Elongation Strength ElongationYoung's Gardner At Yield At Yield At Break At Break Modulus ImpactDensity Formula (psi) (psi) (psi) (psi) (psi) In-lbs Tg g/cc 1 9190 7.46710 57 268,000 600 99.1 1.091 2 9530 7.5 7030 65 282,000 592 102 1.0933 12,100 9.2 9040 41 336,000 120 126 1.14 4 11,200 8.7 8230 38 321,000190 119 1.13 5 13,100 9.6 11,000 19 351,000 71 140 1.13 6 11,000 8.78300 56 311,000 130 117 1.12 7 13,600 10 12,100 18 360,000 75 156 1.13 812,100 9.8 9380 32 339,000 143 132 1.12 9 11,900 9.4 8880 34 327,000 124130 1.14 10 9880 7.9 7480 55 287,000 600 106 1.10 11 — — — — — 65 — —

Example R18

This example was conducted in accordance with the procedure in Example12 with the exceptions that 53.0 equivalent wt. of diethylene glycol wasused instead of ethylene glycol and the mixture was heated to atemperature of 115° C. instead of 105° C.

The impact was measured as 6.0 in-lbs.

Example R19

This example was conducted in accordance with the procedure in Example18 with the exception that 67.0 equivalent wt. dipropylene glycol wasused instead of diethylene glycol.

The impact was measured as 8.0 in-lbs.

After curing, a set of the sheets coated with each of the polymers A-Dwere abrasion tested using a standard Taber abrasion test with CS10Fwheels (one pair for all samples), 500 grams each wheel. The wheels werere-surfaced before each cycle (25 cycles). Test conditions wereconducted at a temperatureh of ranging from about 70° F. to about 75° F.and about 50% to about 60% relative humidity. Average scattered lighthaze for a given number of Taber cycles was determined, with the resultsshown below.

Standard QUV-B exposure test procedure over a period of 1000 hours,representing the equivalent of about three years of outdoor exposure.The results are shown below.

Exposed Samples—1000 hours QUV-B Exposure—3 yr. Equivalent OutdoorCoated with % Haze at number of Cycles Sample 0 100 300 500 1000 PolymerA Polymer B Polymer C Polymer D

Example S

Fire Retardance Testing

Example S1

A polyurethane polymer according to the present invention was preparedfrom the components listed below: Desired Polymer Batch Solids Wt. (g)Size (g) Monomer Tetrabromobisphenol 1,6- TMP Des W 291.54 100.00 Name Abis(2-hydroxyethyl) hexanediol ether OH # — — — — Acid # — — — —Equivalent 315.99 59.09 44.00 131.2 Wt. Equivalents 0.4000 0.5000 0.1001.000 desired Mass 126.40 29.55 4.40 131.20 Monomer Weight % 43.35%10.13% 1.51% 45.00% Monomer Monomer 43.35 10.13 1.51 45.00 masses forexperiment — Weight % 20.24 Urethane Molecular 8746.23 Weight perCrosslink (g/mole) (M_(c)

The 1,6-hexanediol, trimethylolpropane and DESMODUR W preheated to 80°C. were added to a glass beaker along with solid tetrabromobisphenol Abis(2-hydroxyethyl)ether. While stirring on a hotplate, the mixture washeated until the mixture had cleared and all solid tetrabromobisphenol Abis(2-hydroxyethyl)ether had dissolved/melted.

Initial Gardner impact data showed better impact strength than stretchedacrylic (>16 in/lbs), and much higher than PLEXIGLAS (2 in-lb). Burntesting with a Bunsen burner showed that the flame was immediatelyself-extinguishing.

Example S2

A polyurethane polymer according to the present invention was preparedfrom the components listed below: Desired Batch Solids Size (g) MonomerName Tetrabromobisphenol A 1,6- TMP Des W 475.00 bis(2-hydroxyethyl)hexanediol ether OH # — — — — Acid # — — — — Equivalent Wt. 315.99 59.0944.00 131.2 Equivalents 0.4500 0.4500 0.100 1.000 desired Mass Monomer142.20 26.59 4.40 131.20 Weight % 46.72% 8.74% 1.45% 43.10% MonomerMonomer 221.90 41.49 6.87 204.74 masses for experiment — Weight % 19.38Urethane Molecular 9131.58 Weight per Crosslink (g/mole) (M_(c)

The polymer weight was 304.39 grams. The 1,6-hexanediol,trimethylolpropane and DESMODUR W preheated to 80° C. were added to aglass kettle along with solid tetrabromobisphenol Abis(2-hydroxyethyl)ether. Under nitrogen blanket and with constantstirring, the mixture was heated to ˜105° C., until the mixture hadcleared and all solid tetrabromobisphenol A bis(2-hydroxyethyl)ether haddissolved/melted. Once clear, the mixture was degassed, and cast into a12″×12″×0.125″ casting cell preheated to 121° C. The filled cell iscured for 48 hours at 121° C. Initial impact data showed very poorperformance (<16 in/lbs). Burn testing with a Bunsen burner showed thatthe flame was immediately self-extinguishing.

Example S3

A polyurethane polymer according to the present invention was preparedfrom the components listed below: Desired Batch Solids Size (g) MonomerName Tetrabromobisphenol 1,6-hexanediol TMP Des W 300.00 Abis(2-hydroxyethyl) ether OH # — — — — Acid # — — — — Equivalent 315.9959.09 44.00 131.2 Wt. Equivalents 0.1000 0.8000 0.100 1.000 desired Mass31.60 47.27 4.40 131.20 Monomer Weight % 14.73% 22.04% 2.05% 61.17%Monomer Monomer 44.20 66.12 6.15 183.52 masses for experiment — Weight %27.51 Urethane Molecular 6434.13 Weight per Crosslink (g/mole) (M_(c)

The polymer weight was 214.47 grams. The 1,6-hexanediol,trimethylolpropane and DESMODUR W preheated to 80° C. were added to aglass kettle along with solid tetrabromobisphenol Abis(2-hydroxyethyl)ether. Under nitrogen blanket and with constantstirring, the mixture was heated to ˜105° C., until the mixture hadcleared and all solid tetrabromobisphenol A bis(2-hydroxyethyl)ether haddissolved/melted. Once clear, the mixture was degassed, and cast into a12″×12″×0.125″ casting cell preheated to 121° C. The filled cell iscured for 48 hours at 121° C. Burn testing with a Bunsen burner showedthat the polymer charred and burned for about 7 seconds after the flamewas removed.

Example T

Fiberglass Reinforced Polyurethane

The following reactants: 208 grams of 1,10-decanediol (2.39 equivalents)and 45.7 grams of trimethylolpropane (1.02 equivalents) were chargedinto a flask and heated to 125° C. under a nitrogen blanket withstirring. When a clear, homogenous melt was formed the mixture wascooled to 105° C. and 446 grams (3.41 equivalents) of DESMODUR W wereadded. After mixing for 15 minutes and reheating to about 90° C. themixture clarified. After controlling the temperature at 90° C. for about10 minutes, approximately 50% of the liquid was vacuum transferred intoa 20″ by 20″ by ⅛″ (50.8 cm×50.8 cm×0.3 cm) thick mold containing 4layers of bidirectional E-glass fiber mat covered by release fabric andflow mesh inside a vacuum bag. The mold and glass were preheated to 105°C. before beginning the transfer.

After approximately 15 minutes sufficient material was transferred tocompletely fill the bag and wet the fiberglass. The bag and mold werethen heated to 143° C. for 48 hours. The temperature of the resultingfiberglass-urethane composite was then reduced to 120° C. and held for 1hour, followed by a further reduction in temperature to 38° C. After aone hour hold at 38° C. the system was cooled to room temperature anddisassembled. The resulting part was rigid, colorless and void-free.

Example U

Multilayer Composite of Cast Film According to the Present Invention onStretched Acrylic

A casting cell was constructed using 0.5″ Polycast 84® stretched acrylicand 0.25″ of glass that was release coated with dimethyidichlorosilane.A primer was applied to the stretched acrylic for good urethaneadhesion. The cell was 6″×6″ with a 0.060″ gap between the glass and thestretched acrylic held constant with a silicone rubber gasket. The edgeswere clamped. A composition using 0.3 equivalents of trimethylolpropane,0.7equivalents of 1,5 pentanediol, and 1.0 equivalents of DESMODUR Wwere mixed and degassed at 210° F. and poured into the described castingcell. The composition was cured at 180° F. for 3 days, allowed to coolto room temperature, and then the film-cast plastic was separated fromthe glass release plate. A high optical quality composite was producedthat had excellent substrate adhesion and high resistance to solventstress-craze resistance. The composite was stressed to 4,000 psi withthe polyurethane plastic in tensile stress and ethyl acetate wasapplied, covered with a glass cover slip and allowed to sit for 30minutes. No crazing was observed even under microscopic examination. Thesame test was done on bare stretched acrylic in which crazes areimmediately visible without microscopic examination. The same test wasrun on bare stretched acrylic stressed to 1000 psi. Crazing was againimmediately visible without microscopic examination.

Examples V

Reinforced Composites

With reference to Table 30 below, a thermoset polyurethane was preparedas follows:

A reaction vessel was equipped with a stirrer, thermocouple, nitrogeninlet, distillation container and vacuum pump. Charge A was then addedand stirred with heating to 80° C.-100° C. under vacuum and held for 1hour. The reaction mixture was then cooled to 80° C., vacuum turned offand Charge B was added to the vessel. The reaction mixture was thenheated to 80° C. under vacuum and allowed to exotherm from 110° C.-120°C. The reaction mixture was then cast in place between two 5 inch by 5inch by three sixteenths inch float glass plates which were fitted withgaskets on three sides and held together using clamps. Both glass plateshad a silane release coating on their faces that contacted thepolyurethane. The spacing between the plates was approximately threesixteenths of an inch. The casting cell was preheated to a temperatureof about 120° C. before casting. After casting, the assembly was given a24 hour cure at 120° C. and then a 16 hour cure at 143° C. After curingwas complete, the cell was given a two hour gradual cool down cycle fromthe 143° C. temperature to 45° C. while remaining in the oven. The cellwas removed from the oven and the glass plates were separated from thepolyurethane. TABLE 30 Parts by Weight Charge A 1,10-Decanediol 61.00Trimethylolpropane 13.41 Charge B Desmodur W¹ 131.00¹Bis(4-isocyanatocyclohexyl)methane from Bayer Material Science.

Example V

The following Examples show the infusion of various inorganicparticulate phases into a thermoset polymeric phase. The thermosetpolymers were contacted with various swelling solvents and variousprecursors that formed the inorganic particulate phase in situ.

Example V1

Infusion of Tetramethyl Orthosilicate in Methanol

The thermoset polyurethane of Example A was immersed into a solutioncomprising 20.3% by weight (25% by volume) of anhydrous methanol and79.7% by weight (75% by volume) of tetramethyl orthosilicate (TMOS) for24 hours. The poly(urethane) was removed from the methanol/TMOS solutionand placed into deionized water for three days. The poly(urethane) wassubsequently placed in a vacuum oven at 100° C. for 2 hours.Transmission electron microscopy (TEM) indicated that silica particleshad infused into the polyurethane phase. The silica particles hadgenerated 250 μm into the poly(urethane) substrate. Silica nanoparticlemorphology was generally spherical and the particle size ranged from 10to 20 nm. Discrete particles and clusters of particles were seen in thisspecimen.

Example V2

Infusion of Tetraethyl Orthosilicate in Ethanol

The thermoset polyurethane of Example A was immersed into a solutioncomprising 21.9% by weight (25% by volume) of anhydrous ethanol and78.1% by weight (75% by volume) of tetraethyl orthosilicate (TEOS) for24 hours. The poly(urethane) was removed from the ethanol/TEOS solutionand placed into a 14% aqueous solution of ammonium hydroxide for fourhours. The poly(urethane) was rinsed with water and placed into an ovenat 143° C. for four hours. TEM indicated silica nanoparticles hadinfused into the polyurethane phase. The nanoparticles ranged in sizefrom 10 to 70 nm with most being in the 10 nm range.

Example V3

Infusion of Tetramethyl Orthosilicate in Xylene

The thermoset polyurethane of Example A was immersed into a solutioncomprising 21.7% by weight (25% by volume) of anhydrous xylene and 78.3%by weight (75% by volume) of tetramethyl orthosilicate (TMOS) for 24hours. The poly(urethane) was removed from the xylene/TMOS solution andplaced into a 14% aqueous solution of ammonium hydroxide for four hours.The poly(urethane) was rinsed with water and placed into an oven at 143°C. for four hours. TEM indicated silica nanoparticles had infused intothe polyurethane phase. The nanoparticles ranged in size from 7 to 40nanometers.

Example V4

Infusion of Tetramethyl Orthosilicate in Ethyl Acetate

The thermoset polyurethane of Example A was immersed into a solutioncomprising 22.4% by weight (25% by volume) of anhydrous ethyl acetateand 77.6% by weight (75% by volume) of tetramethyl orthosilicate (TMOS)for 24 hours. The poly(urethane) was removed from the ethyl acetate/TMOSsolution and placed into a 14% aqueous solution of ammonium hydroxidefor four hours. The poly(urethane) was rinsed with water and placed intoan oven at 143° C. for four hours. TEM indicated silica nanoparticleshad infused into the polyurethane phase.

Example V5

Infusion of Tetramethyl Orthosilicate in Dimethyl Sulfoxide

The polyurethane of Example A was immersed into a solution comprising25% by weight (25% by volume) of anhydrous dimethyl sulfoxide (DMSO) and75% by weight (75% by volume) of tetramethyl orthosilicate (TMOS) for 24hours. The poly(urethane) was removed from the DMSO/TMOS solution andplaced into a 14% aqueous solution of ammonium hydroxide for four hours.The poly(urethane) was rinsed with water and placed into an oven at 143°C. for four hours. TEM indicated silica nanoparticles had infused intothe polyurethane phase. The nanoparticles ranged in size from 7 to 30nanometers.

Example V6

Infusion of Tetramethyl Orthosilicate into a Crosslinked Polvester Film

A piece of crosslinked polyester film was immersed into a solutioncomprising 20.3% by weight (25% by volume) of anhydrous methanol and79.7% by weight (75% by volume) of tetramethyl orthosilicate (TMOS) fortwo hours. The film was removed from the methanol/TMOS solution andplaced into a 14% aqueous solution of ammonium hydroxide for two hours.The film was rinsed with water for 15 minutes and allowed to dry at roomtemperature for 17 hours. A silica particulate phase infused into thepolymeric phase. TEM indicated the nanoparticles ranged in size from 7to 300 nm.

Example V7

Infusion of Titanium Bis(ethyl acetoacetato) Diisopropoxide in EthylAcetate

The thermoset polyurethane of Example A was immersed into a solutioncomprising 80.1% by weight of anhydrous ethyl acetate and 19.9% byweight of titanium bis(ethyl acetoacetato) diisopropoxide for 24 hours.The poly(urethane) was removed from the ethyl acetate/titanium bis(ethylacetoacetato) diisopropoxide solution and placed into a 14% aqueoussolution of ammonium hydroxide for four hours. The poly(urethane) wasrinsed with water and placed into an oven at 143° C. for four hours. Atitania particulate phase infused into the polyurethane phase. Temindicated the nanoparticles ranged in size from 5 to 200 nm.

Example V8

Infusion of Zirconium(IV) Acetylacetonate in Ethyl Acetate

The thermoset polyurethane of Example A was immersed into a solutioncomprising 91.2% by weight of anhydrous ethyl acetate and 8.8% by weightof zirconium(IV) acetylacetonate for 24 hours. The poly(urethane) wasremoved from the ethyl acetate/zirconium(IV) acetylacetonate solutionand placed into a 14% aqueous solution of ammonium hydroxide for fourhours. The poly(urethane) was rinsed with water and placed into an ovenat 143° C. for four hours. A zirconia particulate phase infused into thepolyurethane phase.

Examples W

Synthesis of Acrylic Silane Polymers

For each of Examples A to C in Table 23, a reaction flask was equippedwith a stirrer, thermocouple, nitrogen inlet and a condenser. Charge Awas then added and stirred with heat to reflux temperature (75° C.-80°C.) under nitrogen atmosphere. To the refluxing ethanol, charge B andcharge C were simultaneously added over three hours. The reactionmixture was held at reflux condition for two hours. Charge D was thenadded over a period of 30 minutes. The reaction mixture was held atreflux condition for two hours and subsequently cooled to 30° C. TABLE31 Example A Example B Example C Charge A (weight in grams) Ethanol SDA40B¹ 360.1 752.8 1440.2 Charge B (weight in grams) Methyl Methacrylate12.8  41.8 137.9 Acrylic acid 8.7  18.1 34.6 Silquest A-174² 101.4 211.9405.4 2-hydroxylethylmethacrylate 14.5  0.3 0.64 n-Butyl acrylate 0.2 0.3 0.64 Acrylamide 7.2 — — Sartomer SR 355³ —  30.3 — Ethanol SDA 40B155.7 325.5 622.6 Charge C (weight in grams) Vazo 67⁴ 6.1  12.8 24.5Ethanol SDA 40B 76.7 160.4 306.8 Charge D (weight in grams) Vazo 67 1.5 2.1 6.1 Ethanol SDA 40B 9.1  18.9 36.2 % Solids 17.9  19.5 19.1 Acidvalue (100% resin 51.96  45.64 45.03 solids) Mn — 3021⁵   5810¹Denatured ethyl alcohol, 200 proof, available from Archer DanielMidland Co.²gamma-methacryloxypropyltrimethoxysilane, available from GE silicones.³Di-trimethylolpropane tetraacrylate, available from Sartomer CompanyInc.⁴2,2′-azo bis(2-methyl butyronitrile), available from E.I. duPont deNemours & Co., Inc.⁵Mn of soluble portion; the polymer is not completely soluble intetrahydrofuran.

Example W1

The acrylic-silane resin from Example A (8.5 grams) was blended withpolyvinylpyrrolidone (0.1 grams) and water (1.5 grams). The formulationwas stored at room temperature for 225 minutes. A portion of theresulting solution was loaded into a 10 ml syringe and delivered via asyringe pump at a rate of 1.6 milliliters per hour to the spinneret asdescribed in Example 1. The conditions for electrospinning were asdescribed in Example 1. Ribbon shaped nanofibers having a thickness of100-200 nanometers and a width of 1200-5000 nanometers were collected ongrounded aluminum foil and were characterized by optical microscopy andscanning electron microscopy. A sample of the nanofiber was dried in anoven at 110° C. for two hours. No measurable weight loss was observed.This indicates the nanofibers were completely crosslinked.

Examples W2 and W3

Transparent composite articles comprising a polyurethane matrix andelectrospun fibers of Example 1 were prepared as follows:

For each of Examples 2 and 3, see Table 32 below, a reaction vessel wasequipped with a stirrer, thermocouple, nitrogen inlet, distillationcontainer and vacuum pump. Charge A was then added and stirred withheating to 80° C.-100° C. under vacuum and held for 1 hour. The reactionmixture was then cooled to 80° C., vacuum turned off and Charge B wasadded to the vessel. The reaction mixture was then heated to 80° C.under vacuum and allowed to exotherm from 110° C.-120° C. The reactionmixture was then cast in place between two 5 inch by 5 inch by threesixteenths inch float glass plates which were fitted with gaskets onthree sides and held together using clamps. Both glass plates had asilane release coating on their faces that contacted the electrospunfibers and the polyurethane. The fibers were spun over the treatedplates before assembling them into a casting cell. The casting cell wasassembled with the electrospun nanofiber covered plate on the inside ofthe casting cell. The spacing between the plates was approximately threesixteenths of an inch. The casting cell was preheated to a temperatureof about 120° C. before casting. After casting, the assemblies weregiven a 24 hour cure at 120° C. and then a 16 hour cure at 143° C. Aftercuring was complete, the cells were given a two hour gradual cool downcycle from the 143° C. temperature to 45° C. while remaining in theoven. The cells were removed from the oven and the glass plates wereseparated from the composite article.

Polyurethane Examples 2 and 3

TABLE 32 Example 2 Example 3 Charge A (weight in grams) 1,4 Butanediol31.54 — 1,10 Decanediol — 61.00 Trimethylolpropane 13.41 13.41 Charge B(weight in grams) Desmodur W¹ 131.00 131.00¹Bis(4-isocyanatocyclohexyl)methane from Bayer Material Science.

Each composite article was tested for scratch resistance by subjectingthe composite to scratch testing by linearly scratching the surface witha weighted abrasive paper for ten double rubs using an Atlas ATCCScratch Tester, Model CM-5, available from Atlas Electrical DevicesCompany of Chicago, Ill. The abrasive paper used was 3M 281Q WETORDRY™PRODUCTION™ 9 micron polishing paper sheets, which are commerciallyavailable from 3M Company of St. Paul, Minn.

After completing the scratch-test with a Crockmeter using a 9-μmabrasive, the increase in the average roughness in the surface of thescratched area was measured using an optical profilometer. The surfaceof the scratched area was scanned perpendicular to the direction on theCrockmeter scratching; that is, across the scratches. An identical scanwas taken in an unscratched area to measure average roughness of thesurface of the original article. Change in average surface roughness foreach article was calculated by subtracting the average roughness of theunscratched surface from the average roughness of the scratched surface.Transparent articles with no nanofibers were compared with transparentcomposite articles containing electrospun fibers from Example 3.

Also, for the purpose of comparison, composite articles were prepared asgenerally described above for Example 3 but in which polyvinylidenefluoride (KYNAR) and nylon-6 fibers were electrospun and used in placeof the fibers of Example 3. The composite articles were evaluated forscratch resistance as described above. The results of the testing arereported in Table 33 below. TABLE 33 Change in average surface roughnessExample Electrospun Fibers (nm) Control None 74.54 Example 4 Example 36.93 Example 4 (repeat) Example 3 −7.28 Control (repeat) None 81.48Example 5 Example 3 −4.91 Comparative KYNAR 90.2 Comparative Nylon-666.96

The results reported in Table 33 show the improvement in scratchresistance provided by the acrylic-silane electrospun fibers.

Example X Powder Example

1,4-Butanediol (5.47 grams, 0.122 equivalents) and 4,4′-methylenebis-cyclohexylisocyanate (DESMODUR W from Bayer Corporation; NCOequivalent weight 131; 14.52 grams, 0.111 equivalents) were stirredtogether in a dry glass container. One drop of dibutyltin dilaurate wasadded. The cloudy mixture warmed spontaneously and became transparent.The mixture was then placed in an oven at 120° C. for 6 hours.

A 1.88 gram portion of the resulting glassy, solid polyurethane wasdissolved in 5.23 grams of M-Pyrol by boiling on a hot plate. Similarly,isophorone diisocyanate trimer (0.23 grams) was dissolved in 3.68 gramsof M-Pyrol. The two solutions were combined in an aluminum dish andbaked at 145° C. for 35 minutes. The resulting film was transparent,tough and, hard. Rubbing with methyl ethyl ketone did not soften thefilm or cause it to become tacky, indicating it was thoroughlycrosslinked.

Example Y

Liquid Infusion of Inorganic Precursors into Urethane Resulting inIn-Situ Generated Nanoparticles

A piece of urethane plastic was prepared by the following method.Dimethyl dichlorosilane was vapor deposited onto the surface of twopieces of tempered glass and the excess was wiped off with isopropanol.A rubber gasket ( 3/16″ in diameter) was placed between the two piecesof glass and the pieces of glass were fastened together so that one endof the mold was open. The prepolymer was prepared by heating 504 g1,10-decanediol (3.55 mol, 0.7 equivalents) and 111 g trimethylolpropane(0.83 mol, 0.3 equivalents) in a three-neck round bottom flask to 120°C. under vacuum, where it was held for 30 minutes. The contents of theflask were cooled to 80° C. and 1084 g dicyclohexylmethane diisocyanate(4.14 mol, 1 equivalent) was added. The reaction exothermed to 105° C.and the solution was poured into the open end of the glass mold. Themold was placed into an oven at 120° C. for 24 hours and 143° C. for 16hours. The temperature was decreased to 43° C. for one hour and the moldwas removed from the oven. The mold was disassembled to remove the casturethane plastic part.

A solution comprising 75% by volume of tetramethylorthosilicate (TMOS)and 25% by volume of methanol was prepared in a sealed container. Apiece of urethane plastic was placed into the sealed container and thecontainer was flushed with dry nitrogen gas. The urethane plastic soakedin the TMOS/methanol solution for 4 or 24 hours. The urethane plasticwas removed and immersed in: 1) water for 72 hours, 2) 2 M HCl for onehour and water for one hour or 3) 15% v/v solution of NH₄OH in water forone hour and water for one hour. The specimens were subsequentlyannealed at 143° C. for 4 hours. The immersion soaks hydrolyzed andcondensed the liquid inorganic precursor (TMOS) that was infused in theplastic. Each soak resulted in different sized nanoparticles which werelocated at different depths in the plastic.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof. It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications which are within the spirit and scopeof the invention, as defined by the appended claims.

1. A poly(ureaurethane) comprising a reaction product of componentscomprising: (a) at least one polyisocyanate selected from the groupconsisting of polyisocyanate trimers and branched polyisocyanates, thepolyisocyanate having at least three isocyanate functional groups; (b)about 0.1 to about 0.9 equivalents of at least one polyol having 4 to 18carbon atoms and at least 2 hydroxyl groups; and (c) at least one aminecuring agent, wherein the reaction product components are essentiallyfree of polyester polyol and polyether polyol.
 2. The poly(ureaurethane)according to claim 1, wherein the polyisocyanate is a trimer of adiisocyanate selected from the group consisting of hexamethylenediisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate,and mixtures thereof.
 3. The poly(ureaurethane) according to claim 1,wherein the polyisocyanate is a branched polyisocyanate selected fromthe group consisting of2,4,6-trioxo-1,3,5-tris(6-isocyanatohexyl)hexahydro-1,3,5-triazine,2,4,6-trioxo-1,3,5-tris(5-isocyanato-1,3,3-trimethylcyclohexylmethyl)hexahydro-1,3,5-triazine,tris(4-iso-cyanatophenyl)methane,1,3,5-tris(3-isocyanato-4-methylphenyl)-2,3,6-trioxohexahydro-1,3,5triazine, N-isocyanatohexylaminocarbonyl-N,N′-bis(isocyanatohexyl) urea,4-(isocyanatomethyl)-1,8-octane diisocyanate and mixtures thereof. 4.The polyurethane according to claim 1, wherein the polyisocyanate isselected from the group consisting of aliphatic, cycloaliphatic,aromatic and heterocyclic isocyanates, dimers and trimers thereof andmixtures thereof.
 5. The poly(ureaurethane) according to claim 1,wherein the polyisocyanate is present in an amount of about 1 equivalentand the water is present in an amount of about 0.05 to about 0.5equivalents.
 6. The poly(ureaurethane) according to claim 1, wherein thealiphatic polyol is selected from the group consisting of diols, triols,and mixtures thereof.
 7. The poly(ureaurethane) according to claim 6,wherein the aliphatic polyol is a diol selected from the groupconsisting of ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, 1,2-ethanediol, propanediol, butanediol,pentanediol, hexanediol, heptanediol, octanediol, nonanediol,decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol,1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol,xylene glycol, hydroxybenzyl alcohol, dihydroxytoluenebis(2-hydroxyethyl)terephthalate, 1,4-bis(hydroxyethyl)piperazine,N,N′,bis(2-hydroxyethyl)oxamide and mixtures thereof.
 8. Thepoly(ureaurethane) according to claim 7, wherein the diol is selectedfrom the group consisting of butanediol, pentanediol, cyclohexanedimethanol and mixtures thereof.
 9. The poly(ureaurethane) according toclaim 1, wherein the aliphatic polyol is a triol selected from the groupconsisting of glycerol, glycerin, tetramethylolmethane,trimethylolethane, trimethylolpropane, erythritol, pentaerythritol,dipentaerythritol, tripentaerythritol, alkoxylated derivatives thereofand mixtures thereof.
 10. The poly(ureaurethane) according to claim 9,wherein the branched polyol is trimethylolpropane.
 11. Thepoly(ureaurethane) according to claim 1, wherein the aliphatic polyol ispresent in an amount of about 0.1 to about 1 equivalents.
 12. Thepoly(ureaurethane) according to claim 1, wherein the reaction productcomponents are essentially free of polyester polyol
 13. Thepoly(ureaurethane) according to claim 1, wherein the reaction productcomponents are essentially free of polyether polyol.
 14. Thepoly(ureaurethane) according to claim 1, wherein the reaction productcomponents further comprise one or more polyurethane polyols,acrylamides, polyvinyl alcohols, hydroxy functional acrylates, hydroxyfunctional methacrylates, allyl alcohols, dihydroxy oxamides,dihydroxyamides, dihydroxy piperidines, dihydroxy phthalates,dihydroxyethyl hydroquinones and mixtures thereof.
 15. An articlecomprising the poly(ureaurethane) of claim
 1. 16. The article accordingto claim 15, wherein the article is a molded article.
 17. The articleaccording to claim 15, wherein the article is selected from the groupconsisting of transparencies, optical articles, photochromic articles,ballistic resistant articles, and glazings.
 18. A laminate comprising:(a) at least one layer of the poly(ureaurethane) of claim 1; and (b) atleast one layer of a substrate selected from the group consisting ofpaper, glass, ceramic, wood, masonry, textile, metal or organicpolymeric material and combinations thereof.
 19. A coating compositioncomprising the poly(ureaurethane) of claim 1.